Group 4 metal-containing organosilicon dendrimers are described. Also described are methods for synthesizing the dendrimers. The dendrimers can be useful in several applications including as olefin polymerization and copolymerization catalysts and as silane polymerization catalysts.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The invention relates to Group 4 metal-containing organosilicon dendrimers, 
methods of preparation thereof, and methods of use thereof. 
2. Description of the Prior Art 
Dendrimers are chemical compounds characterized by a regular, highly 
branched structure as shown schematically in FIG. 1. Dendrimer 10 of FIG. 
1 is a second generation dendrimer, denoted by a generation number, 
G.sub.n, equal to G.sub.2. Dendrimer 10 includes an initiator core 12 from 
which branches, whose number is denoted by N.sub.n and characterized by 
length l, emanate. Four main branches (N.sub.1 =4) emanate directly from 
initiator core 12 and form four primary branch points 14 from each of 
which three new branches (N.sub.1 =3) emanate and form secondary branch 
points 16 as the next generation polymer is produced. Branches that 
emanate from branch points 16 terminate in end groups 20. 
Dendrimers are ideally monodisperse, i.e., they consist of single, 
identical species, all of which have the same composition and molecular 
weight. Dendrimers can be characterized by a range of molecular weights, 
ranging from relatively low oligomeric molecular weight, to relatively 
high polymeric molecular weights. Dendrimer molecular weights can depend 
on several factors including length of the arms, the extent of arm 
branching, the functionality of the branching groups in the arms, the 
length of connecting groups between branching sites and the functionality 
of the dendrimer core. Typically, dendrimers are soluble in organic 
solvents and their solubility in a particular solvent can be optimized by 
the choice of appropriate functional groups for the end groups. However, 
end groups may be chosen so as to result in water solubility. Dendrimers 
of intermediate generation number, G.sub.n, typically with n in the range 
of from about 1 to about 10, depending upon the dendrimer system, are 
characterized by an uncongested periphery with empty space between 
neighboring end groups. As such, intermediate generation number dendrimers 
have high surface areas and a relatively large proportion of unoccupied 
dendrimer interior volume. 
Dendrimers can be synthesized using a "divergent procedure", according to 
which dendrimers are grown outward by repetitive chemical steps using a 
multifunctional central core molecule as the starting material. According 
to this approach, successive hydrosilylation and vinylation, or 
alternatively, allylation, steps are performed on the polyfunctional core, 
which can be a tetravinylsilane or tetrallylsilane to form the dendrimeric 
structure. The divergent procedure is reliable and effective, provided 
that appropriate reaction conditions are maintained until that point in 
the synthesis when steric congestion at the dendrimer periphery hinders 
further dendrimer growth. However, the divergent procedure is multistep, 
relatively expensive and, hence, may not ideally suited for large scale 
commercial applications. 
Alternatively, a "convergent procedure" can be used to synthesize 
dendrimers by preparing segments of the dendrimer first and then attaching 
the segments to a central core molecule. However, the convergent procedure 
is also multistep, relatively expensive and, hence, may not be ideally 
suited for large scale commercial applications. 
A third approach for dendrimer synthesis is a "cascade procedure". 
According to this approach, a single monomer is used in a single type of 
reaction to prepare the dendrimer. Generally, a cascade procedure begins 
with a monomer containing two different reactive functions, x and y, more 
specifically, one x function and two or more y functions. The x and y 
functions are selected so that x can react with y, but not with itself. 
The reaction between x and y is initiated so that branching growth occurs 
to produce a dendrimer. The structure of the dendrimers produced according 
to a cascade procedure will not be as regular a structure as that of 
dendrimers synthesized according to a divergent or convergent procedure. 
Dendrimers produced using the cascade procedure will be polydisperse 
rather than monodisperse and have been referred to as "hyperbranched" 
materials. Typically, the cascade procedure is relatively inexpensive and 
well-suited to large scale commercial applications. 
A type of organosilicon dendrimers, carbosilane dendrimers, and their 
preparation are described in Seyferth et al., Organometallics, 13 (1994) 
2682-2690. A typical dendrimer prepared in the foregoing study is shown in 
FIG. 2. 
Thus, it would be highly desirable to exploit the foregoing dendrimer 
characteristics, including relatively high surface area and relatively 
high porosity, for applications including catalysis by preparation of 
dendrimers having end or interior group substituents with a desired 
chemical activity. Moreover, it would be highly desirable to exploit the 
foregoing desirable cascade procedure characteristics for the synthesis of 
organosilicon dendrimers. 
SUMMARY OF THE INVENTION 
Many of the foregoing needs are met by an organosilicon dendrimer with one 
or more dendrimer arms containing a Group 4 metal such as Ti, Zr, or Hf or 
mixtures thereof. The invention provides dendrimers with Group 4 
metal-containing end or interior group substituents, methods for making 
the dendrimers and polymerization methods that use the Group 4 
metal-containing dendrimers as catalysts. 
According to one aspect of the invention, a method for synthesizing such a 
dendrimer including a Group 4 metal substituent is provided. The method 
includes steps of (a) providing a core molecule containing one or more 
reactive functional groups; (b) providing a silicon hydride with an 
appropriate reactive functionality such as a silicon-halogen bond; (c) 
providing a hydrosilylation catalyst; (d) reacting the silicon hydride 
with the core molecule in the presence of the hydrosilylation catalyst to 
produce an intermediate organosilicon dendrimer; (e) reacting the 
intermediate organosilicon dendrimer to introduce an unsaturated organic 
functional group; (f) repeating steps (b), (c), (d), and (e) n times using 
the intermediate organosilicon dendrimer as formed in step (e) as the core 
molecule to produce a G.sub.n generation organosilicon dendrimer wherein n 
is an integer in the range of from about 1 to about 10 and G.sub.n is the 
generation number; and (g) reacting the G.sub.n generation organosilicon 
dendrimer with a Group 4 metal-containing reagent to form an organosilicon 
dendrimer including a Group 4 metal. 
Another aspect of the invention provides a method for polymerizing an 
olefin including steps of contacting olefin monomers with an organosilicon 
dendrimer catalyst including a Group 4 metal, such as Ti, Zr, or Hf, or 
mixtures thereof, so that the olefin monomers are polymerized to form a 
polyolefin. 
Yet another aspect of the invention is a dehydrogenative condensation 
polymerization of silane monomers, RSiH.sub.3, to form a polysilane using 
the dendrimers of the invention as a catalyst. 
In yet another aspect of the invention, such a cascade procedure includes 
steps of providing starting monomers including a Si--H bond and at least 
two functional groups that each include a terminal .dbd.CH.sub.2 bond, 
inducing a hydrosilylation reaction to consume the monomers, thereby 
producing an intermediate organosilicon dendrimer and reacting the 
intermediate organosilicon dendrimer with a Group 4 metal-containing 
reagent to form a Group 4 metal-containing organosilicon dendrimer. 
In still another aspect of the invention, a core-based cascade procedure 
for synthesizing a Group 4 transition metal-containing organosilicon 
dendrimer is provided. According to the method, a core molecule such as, 
but not limited to, Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 with 
n=0-20; RSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 where n=0-20 and R is 
an alkyl, aryl, halogen, alkoxy or aryloxy group or the like; Si[C.sub.6 
H.sub.4 (CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 where n=0-20 and C.sub.6 
H.sub.4 is para-phenylene or meta-phenylene or the like; and Rsi[C.sub.6 
H.sub.4 (CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 where n=0-20 and R is 
alkyl, aryl, halogen, alkoxy or aryloxy or the like; and C.sub.6 H.sub.4 
is para-phenylene or meta-phenylene or the like is the starting material. 
A first reagent such as, but not limited to, HSi(CH.dbd.CH.sub.2).sub.3 ; 
HSi(CH.sub.2 CH.dbd.CH.sub.2).sub.3 ; HSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 
].sub.3, where n=2-20; R(H)Si(CH.dbd.CH.sub.2).sub.2 ; R(H)Si(CH.sub.2 
CH.dbd.CH.sub.2).sub.2 ; or R(H)Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 
].sub.2, where n=2-20, R is methyl or higer alkyl, phenyl or substituted 
phenyl, halogen, alkoxy, aryloxy or dialkylamino groups or the like is 
added to the core molecule to form an intermediate product. Additional 
reagent such as, but not limited to, HSi(CH.dbd.CH.sub.2).sub.3 ; 
HSi(CH.sub.2 CH.dbd.CH.sub.2).sub.3 ; HSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 
].sub.3, where n=2-20; R(H)Si(CH.dbd.CH.sub.2).sub.2 ; or R(H)Si(CH.sub.2 
CH.dbd.CH.sub.2).sub.3 ; R(H)Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.2, 
where n=2-20, R is methyl or higher alkyl, phenyl or substituted phenyl, 
halogen, alkoxy, aryloxy or dialkylamino groups or the like, is added to 
the intermediate product to form an intermediate organosilicon dendrimer. 
Finally, the intermediate organosilicon dendrimer is reacted with a Group 
4 metal-containing reagent to form an organosilicon dendrimer including a 
Group 4 metal. 
In a further aspect of the invention a core-based synthesis of a Group 4 
metal-containing dendrimer having a desired functionality at an internal 
location within, rather than at the periphery of the dendrimer, is 
provided. The method includes steps of providing a core molecule such as 
Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 where n=0-20; 
RSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 where n=0-20 and R is an 
alkyl, aryl, halogen, alkoxy or aryloxy group. The core molecule is then 
reacted with a first reagent such as [CH.sub.2 .dbd.CH(CH.sub.2).sub.n 
].sub.2 C.sub.6 H.sub.5 SiH, where n=0-20 to form an intermediate product. 
The intermediate product is reacted with a second reagent such as 
[CH.sub.2 .dbd.CH(CH.sub.2).sub.n ].sub.3 SiH; or [CH.sub.2 
.dbd.CH(CH.sub.2).sub.n ].sub.2 SiRH, where R is alkyl and n=0-20 to form 
an intermediate dendrimer by the cascade procedure including reactive 
dendrimer arm ends. A third reagent such as R.sub.2 SiHX where R is an 
alkyl group is then added to react with the reactive dendrimer arm ends of 
the intermediate dendrimer to form peripheral Si--X dendrimer arm ends 
wherein X is F, Cl, Br, or I. The peripheral Si--X dendrimer arm ends are 
reduced to form Si--H peripheral dendrimer arm ends. The Si--X dendrimer 
arm ends can be reduced using LiAlH.sub.4 or other suitable reducing 
agent. The Si--H peripheral dendrimer arm ends are reacted with a reagent 
including a terminal olefin group to form a second intermediate dendrimer. 
The second intermediate dendrimer is reacted with HX, where X is O.sub.3 
SCF.sub.3 or Br, to form a dendrimer having a Si--X internal 
functionality, by cleavage of the Si--C.sub.6 H.sub.5 bond. The dendrimer 
having a Si--X internal functionality is reduced with a reducing agent to 
form a dendrimer having a Si--H internal functionality. Finally, the 
dendrimer having a Si--H internal functionality is reacted with a Group 4 
metal-containing reagent to form an organosilicon dendrimer including an 
internal Group 4 metal functionality. 
In a further aspect of the invention, the foregoing synthesis method is 
modified by instead of reducing the peripheral Si--X dendrimer arm ends to 
form Si--H dendrimer arm ends and then reacting the Si--H dendrimer arm 
ends with a reagent including a terminal olefin group, the Si--X bonds are 
alkylated with RMgX or RLi where R is an alkyl group and X is Cl, Br or I. 
In still a further aspect of the invention, the already-described 
core-based synthesis method for an internally functionalized dendrimer is 
modified by growing the core molecule out to a larger core size by 
reacting the core molecule with [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ]R.sub.2 
SiH where R is a methyl or alkyl group and n=0-20 or [CH.sub.2 
.dbd.CH(CH.sub.2).sub.n ].sub.2 SiH to form an intermediate product 
followed by reacting the intermediate product with [CH.sub.2 
.dbd.CH(CH.sub.2).sub.n ].sub.2 C.sub.6 H.sub.5 SiH to form a second 
intermediate product which is further treated as has already been 
described. 
According to another aspect of the invention a method is provided for 
synthesizing a carbosilane dendrimer using a cascade procedure. The method 
includes steps of providing starting monomers including a Si--H bond and 
at least two functional groups that each include a terminal .dbd.CH.sub.2 
bond, inducing a hydrosilylation reaction to consume the monomers, thereby 
producing an intermediate organosilicon dendrimer including a reactive 
CH.dbd.CH.sub.2 group. A reagent characterized by the general formula 
R.sub.2 SiHX where R is Me, Et, higher alkyl, or aryl or the like and X is 
F, Cl, Br, I and alkoxy or the like is added to the intermediate 
dendrimer, reducing the Si--X bond to produce a reactive Si--H bond. The 
reactive Si--H bond is then reacted with an organic compound including an 
unsaturated carbon-carbon bond such as an olefinic or acetylenic bond to 
form a carbosilane dendrimer. 
In yet another aspect of the invention, a core-based cascade procedure for 
synthesizing a Group 4 transition metal-containing organosilicon dendrimer 
is provided. According to the method, a core molecule such as, but not 
limited to, Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 with n=0-20; 
RSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 where n=0-20 and R is an 
alkyl, aryl, halogen, alkoxy or aryloxy group or the like; Si[C.sub.6 
H.sub.4 (CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 where n=0-20 and C.sub.6 
H.sub.4 is para-phenylene or meta-phenylene or the like; or RSi[C.sub.6 
H.sub.4 (CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 where n=0-20 and R is 
alkyl, aryl, halogen, alkoxy or aryloxy or the like; and C.sub.6 H.sub.4 
is para-phenylene or meta-phenylene or the like is the starting material. 
A first reagent such as, but not limited to, HSi(CH.dbd.CH.sub.2).sub.3 ; 
HSi(CH.sub.2 CH.dbd.CH.sub.2).sub.3 ; HSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 
].sub.3, where n=2-20; R(H)Si(CH.dbd.CH.sub.2).sub.2 ; R(H)Si(CH.sub.2 
CH.dbd.CH.sub.2).sub.2 or R(H)Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.2, 
where n=2-20, R is methyl or higher alkyl, phenyl or substituted phenyl, 
halogen, alkoxy, aryloxy or dialkylamino groups or the like is added to 
the core molecule to form an intermediate product. Additional reagent such 
as HSi(CH.dbd.CH.sub.2).sub.3 ; HSi(CH.sub.2 CH.dbd.CH.sub.2).sub.3 ; 
HSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3, where n=2-20; 
R(H)Si(CH.dbd.CH.sub.2).sub.2 ; R(H)Si(CH.sub.2 CH.dbd.CH.sub.2).sub.2 ; 
R(H)Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.2, where n=2-20, R is methyl 
or higher alkyl, phenyl or substituted phenyl, halogen, alkoxy, aryloxy or 
dialkylamino groups or the like and (CH.sub.2 .dbd.CHCH.sub.2).sub.2 
(CH.sub.3)SiH is added to the intermediate product to form an intermediate 
organosilicon dendrimer including a terminal CH.dbd.CH.sub.2. A reagent 
characterized by the general formula R.sub.2 SiHX where R is Me, Et, 
higher alkyl, or aryl or the like and X is F, Cl, Br, I and alkoxy or the 
like and including a Si--X bond is added to the intermediate dendrimer, 
reducing the Si--X bond to produce a reactive Si--H bond. The reactive 
Si--H bond is then reacted with an organic compound including an 
unsaturated carbon-carbon bond such as an olefinic or acetylenic bond to 
form a carbosilane dendrimer.

DESCRIPTION OF PREFERRED EMBODIMENTS 
The Group 4 metal-containing organosilicon dendrimers can be carbosilanes 
or siloxanes or hybrids thereof. As used herein in the specification and 
claims, a "carbosilanell is an organosilicon compound with organic bridges 
between the silicon atoms. The bridges can be alkylene, such as --CH.sub.2 
--, --CH.sub.2 CH.sub.2 --, --(CH.sub.2).sub.n --, or substituted variants 
thereof; alkenylene, such as --CH.dbd.CH--, --CH.dbd.CH--CH.dbd.CH--, or 
substituted variants thereof; mixed alkylene/alkenylene, such as 
--CH.sub.2 CH.dbd.CHCH.sub.2 --; arylene, such as 
##STR1## 
and substituted variants thereof; or heterocyclic groups such as 
##STR2## 
where Z is O, S, NH or NR and R is alkyl or aryl or the like. Carbosilanes 
are further defined and described in Seyferth, "Polycarbosilanes: An 
Overview", in Inorganic and Organometallic Polymers, (ACS Symposium Series 
360), M. Zeldin et al., eds., American Chemical Society, Washington, D.C., 
1988, pp. 21-42. 
Organosilicon dendrimers that can be used in the present invention include, 
but are not limited to, the organosilicon dendrimers that will be 
described below. The following references are incorporated by reference. 
An organosilicon dendrimer or dendrimers grown from a tetraallylsilane 
core via successive hydrosilylation and allylation steps as described in 
A. W. van der Made et al., J. Chem. Soc., Chem. Commun. (1992) 1400-1401 
can be used. Alternatively, an organosilicon dendrimer or dendrimers grown 
from a 1,3,5-(CH.sub.2 .dbd.CHMe.sub.2 Si).sub.3 C.sub.6 H.sub.3 core via 
successive hydrosilylation/vinylation or allylation steps can be used. A 
hybrid carbosilane/siloxane dendrimer or dendrimers grown by catalyzed 
oligomerization of CH.sub.2 .dbd.CHSI (OSiMe.sub.2 H).sub.3 as described 
in L. J. Mathias et al., J. Am. Chem. Soc., 113 (1991) 4043-4044 or of 
HSi(OSiMe.sub.2 CH.dbd.CH.sub.2).sub.3 as described in S. Rubinsztain, J. 
Inorg. Organomet. Polym., 4 (1994) 61-72 can be used. Finally, a siloxane 
dendrimer or dendrimers such as those described in H. Uchida et al., J. 
Am. Chem. Soc., 112 (1990) 7077-7079 and in A. Morikawa, et al., 
Macromolecules, 24 (1991) 3469-3474 can be used. 
A Group 4 metal-containing organosilicon dendrimer of the present invention 
can be further characterized by a dendrimer arm end, i.e., that portion of 
the dendrimer arm farthest away from the core of the dendrimer, and the 
metal-containing unit can be located at the dendrimer arm end and, thus, 
at the periphery of the dendrimer. 
Alternatively, the Group 4 metal-containing unit can be located at the 
dendrimer arm interior, i.e., at a position intermediate between the 
dendrimer core and the dendrimer periphery. 
The Group 4 metal-containing unit can be a metallocene unit such as a 
bis(cyclopentadienyl) complex metallocene unit or substituent having the 
formula 
##STR3## 
wherein Z is a chalcogen, halide, alkyl, aryl, amide, alkenyl or alkynyl 
substituent, M is the Group 4 metal and 
##STR4## 
denotes a bond connecting the metallocene unit to the dendrimer arm. 
The chalcogen substituent can be an O.sub.2 CR, OR, O.sub.3 SCF.sub.3, or 
SR group wherein R is an organic substituent such as alkyl, 
polyfluoroalkyl, alkenyl, or aryl. The halide substituent can be a F, Cl, 
Br or I ion or mixtures thereof 
The metallocene unit can also be of the formula 
##STR5## 
further including an R substituent wherein the number of such 
substituents, n, is an integer in the range of from about 1 to about 5 and 
R is an alkyl group such as a methyl group or an aryl group such as a 
phenyl or benzyl group. As used herein in the specification and claims, Me 
represents a methyl group and Ph represents a phenyl group. 
Alternatively, the metallocene unit can be characterized by the formula 
##STR6## 
which further includes an R substituent where m, the number of such 
substituents, is an integer in the range of from about 1 to about 4 and R 
is an alkyl group such as a methyl group or an aryl group such as a phenyl 
or benzyl group. 
The metallocene unit can also include a bridging group represented by 
##STR7## 
and have the formula 
##STR8## 
where R is an alkyl or aryl group, n=0-3 and m=0-4. The bridging group can 
be an organic bridge group such as CH.sub.2, CH.sub.2 CH.sub.2, CH.sub.2 
CH.sub.2 CH.sub.2, CMe.sub.2, or Me.sub.2 CCMe.sub.2, CH.dbd.CH, and the 
like. The bridging group can also be an organosilicon bridge such as 
SiMe.sub.2, SiMe.sub.2 CH.sub.2 SiMe.sub.2, SiMe.sub.2 CH.sub.2 CH.sub.2 
SiMe.sub.2, Me.sub.2 SiSiMe.sub.2, or Me.sub.2 SiOSiMe.sub.2 and the like. 
The metallocene unit can also further include a functional group 
represented by 
##STR9## 
and have the formula 
##STR10## 
wherein 
##STR11## 
is a group bonded to the dendrimer such as MeSiCH.sub.2 CH.sub.2 
SiMe.sub.2, MeSiCH.sub.2 SiMe.sub.2, MeSi, PhSi, MeSiSiMe.sub.2, 
MeSiOSiMe.sub.2 and the like, R is an alkyl or aryl group, m=0-4 and 
n=0-4. 
The metallocene unit can also be characterized by the formula 
##STR12## 
The organosilicon dendrimer of the present invention can include a 
monocyclopentadienyl unit metallocene unit having the formula 
##STR13## 
wherein Z is a group such as a chalcogen, halide, alkyl, aryl or amide 
substituent, M is the Group 4 metal, and 
##STR14## 
denotes a bond connecting the metallocene unit to the dendrimer arm and R 
is a group such as methyl, alkyl, or aryl and n is an integer from 0 to 
about 4. 
The dendrimer of the present invention can include a metallocene unit 
characterized by the formula 
##STR15## 
wherein Z is a chalcogen, halide, alkyl, aryl, or amide substituent, M is 
the Group 4 metal, and 
##STR16## 
denotes a bond connecting the metallocene unit to the dendrimer arm. 
The metallocene unit also can be characterized by the formula 
##STR17## 
wherein Z is a chalcogen, halide, alkyl, aryl, or amide substituent, M is 
the Group 4 metal 
##STR18## 
denotes a bond connecting the metallocene unit to the dendrimer arm, and 
##STR19## 
represents a 
##STR20## 
group wherein R is a group such as methyl, isopropyl, t-butyl, alkyl, 
phenyl, or aryl and n=0-3. 
The metallocene unit can have the formula 
##STR21## 
wherein Z is a chalcogen, halide, alkyl, aryl, or amide substituent, M is 
the Group 4 metal, 
##STR22## 
denotes a bond connecting the metallocene unit to the dendrimer arm, 
##STR23## 
represents a 
##STR24## 
group wherein R is a group such as methyl, isopropyl, t-butyl, alkyl, 
phenyl, or aryl. 
Alternatively, the metallocene unit can be further characterized by the 
formula 
##STR25## 
wherein Z can be a chalcogen, halide, alkyl, aryl, or amide substituent, M 
is a Group 4 metal, 
##STR26## 
denotes a bond connecting the metallocene unit to the dendrimer arm, 
##STR27## 
represents a group such as 
##STR28## 
groups, R is a methyl, isopropyl, t-butyl, alkyl, or ary group, and n is 
an integer in the range of from about 0 to about 3. 
The foregoing dendrimers can be chemically attached to a solid support 
phase such as a refractory oxide like alumina, silica or zirconia, or an 
insoluble polymer like cross-linked polystyrene. The solid support phase 
can be selected depending upon the dendrimer catalytic properties desired. 
Several processes exist to prepare an organosilicon, such as a carbosilane, 
dendrimer intermediate of a desired generation number, G.sub.n, to which 
the metal-containing, such as a metallocene, substituent can then be 
attached. In one embodiment, the carbosilane dendrimer growth chemistry is 
based upon a repetitive hydrosilylation/alkenylation sequence as described 
in Seyferth et al., Organometallics, 13 (1994) 2682-2690 where the 
dendrimer was grown out to the fourth generation. Alternatively, a cascade 
synthesis method may be used as described herein. 
Hydrosilylation/Alkenylation Method 
The following describes certain aspects of the present invention with 
respect to hydrosilylation/alkenylation methods of forming group 4 
metal-containing organosilicon dendrimers. 
Silicon hydrides appropriate for use in the hydrosilylation reaction 
include, but are not limited to, HSiCl.sub.3, CH.sub.3 SiHCl.sub.2, 
(CH.sub.3), SiHCl, ClCH.sub.2 (CH.sub.3)SiHCl, 
PhSiHCl.sub.2,HSi(OR).sub.3, CH.sub.3 SIH.sub.2 (OR).sub.2, 
(CH.sub.3).sub.2 SiH(OR).sub.2 or PhSiH OR).sub.2, wherein R is a methyl 
or higher alkyl group. The hydrosilylations can be catalyzed by 
platinum-based catalysts such as H.sub.2 PtCl.sub.6 .multidot.6H.sub.2 O, 
the Karstedt catalyst and other homogeneous Pt catalysts, as well as 
heterogeneous catalysts such as Pt on charcoal or asbestos. Other 
transition metal catalysts can be used, as can free radical initiators 
such as organic peroxides and azo compounds. The reagents used in the 
alkenylation step can include, but are not limited to, Grignard reagents 
such as CH.sub.2 .dbd.CHMgBr; or CH.sub.2 .dbd.CH(CH.sub.2).sub.n 
MgCl.sub.3, n=1-11; organolithium reagents such as CH.sub.2 .dbd.CHLi; or 
CH.sub.2 .dbd.CH(CH.sub.2).sub.n Li, n=-11. Alkynyl-metal reagents such as 
HC.dbd.CNa; HC.dbd.CMgBr; or HC.dbd.C(CH.sub.2).sub.n MgBr, n=1-11 can 
also be used. Use of alkynyl-metal reagents for the hydrosilylation 
results in an alkenylene bridge rather than an alkylene bridge between the 
silicon atoms. 
The carbosilane dendrimer prepared according to the foregoing method is 
then reacted with an appropriate Group 4 metallocene-containing reagent to 
form a carbosilane dendrimer having arms terminating in Group 4 
metallocene substituents. The G.sub.n generation carbosilane dendrimer to 
be reacted with the Group 4 metallocene-containing reagent by a catalyzed 
hydrosilylation reaction can include a dendrimer arm end that terminates 
in a Si--H group. The Si--H containing group can be a --SiMe.sub.2 H, 
--SiMeClH, --SiMeH.sub.2, --SiCl.sub.2 H, --SiPhClH, or SiPhH.sub.2 group. 
The Group 4 metallocene substituent-containing reagent to be reacted with 
the foregoing G.sub.n generation carbosilane dendrimer can contain an 
unsaturated organic functional group wherein carbon is multiply bonded, 
such as C.dbd.C, C.dbd.C, C.dbd.N, or C.dbd.O, that can be bonded to the 
metallocene reactant either directly or via other intervening atoms. 
The metallocene-containing reagent can be chosen from among, but is not 
limited to, the reagents represented by the following formulas. 
##STR29## 
wherein Z can be a chalcogen, halide, alkyl, aryl, amide, alkenyl or 
alkynyl substituent, M is the Group 4 metal, R is a group such as methyl, 
alkyl, phenyl, or aryl, and .fwdarw. represents an electron pair donor 
bond. Z can be a halide such as F, Cl, Br or I, a chalcogen such as O, OR, 
S, SR, or an amide such as NR, where R as already described. Typically, 
the dihalide is used. Each formula is identified by a Roman numeral which 
will be used for reference elsewhere in the specification. In certain 
embodiments, the metallocene substituent-containing reagent can include a 
metallocene substituent such as those given by the following formulas 
##STR30## 
Alternatively, the G.sub.n generation organosilicon dendrimer arm end can 
terminate in a dendrimer unsaturated organic functional group and the 
Si--H containing functional group can be on the metal-containing reagent. 
The unsaturated organic functional group can be a group such as CH.sub.2 
.dbd.CH, CH.sub.2 .dbd.CH(CH.sub.2).sub.n, CH.sub.2 .dbd.CHC.sub.6 
H.sub.4, HC.dbd.C, or HC.dbd.C(CH.sub.2).sub.n, where n=1-11. The 
metal-containing reagent Si--H group can then be reacted with the 
dendrimer unsaturated organic functional group by a catalyzed 
hydrosilylation reaction. Metallocene substituent-containing reagents can 
be given by formulas XII, XIII, XIV, and the like. 
##STR31## 
wherein Z is a chalcogen, halide, alkyl, aryl, or amide substituent, and M 
is the Group 4 metal. 
The metallocene reagent can also be 
##STR32## 
wherein Z is a chalcogen, halide, alkyl, aryl, or amide substituent, M is 
the Group 4 metal, R is a group such as alkyl, or aryl, n=0-4, and m=0-5. 
Here, the metallocene is connected to the dendrimer arms by carbonyl group 
hydrosilylation and the linkage is through an Si--O bond via Si--H 
addition to the C.dbd.O bond. 
A Group 4 metal-containing group, such as a metallocene substituent, can be 
introduced at an internal site or sites in the dendrimer. As used herein 
in the specification and claims, an "internal site" is a position on a 
dendrimer arm intermediate between the dendrimer core and the end of the 
dendrimer arm or dendrimer periphery. The Group 4 metal-containing group 
can be introduced at an internal site by introducing a reactive 
functionality at a dendrimer internal site and reacting the reactive 
functionality with the Group 4 metal-containing reagent so that the Group 
4 metal is introduced at the dendrimer internal site. 
For example, internal site metallocene substituent introduction can be 
accomplished using a silicon hydride that contains a cleavable 
substituent, e.g., PhSiHCl.sub.2, wherein the Ph--Si bond is easily 
cleaved, in step (b) of the method for synthesizing the dendrimer followed 
by; (1) building the dendrimer out to a selected G.sub.n generation; (2) 
terminating the dendrimer arm or arms with an unreactive functionality, 
e.g., SiMe.sub.3 ; (3) cleaving the Si--Ph bond or bonds with HX (X.dbd.Br 
or O.sub.3 SCF.sub.3) and reacting the resulting product with LiAlH.sub.4 
(Si--Ph.fwdarw.Si--X.fwdarw.Si--H sequence); and, finally, (3) reacting 
the Si--H product with a CH.sub.2 .dbd.CH containing metallocene, as 
given, e.g., by formulas I, II, IV, V, VI, VII, VIII, IX, or X. Step (2) 
can be performed at the G.sub.n i.e., the second generation stage of 
dendrimer building according to step (1). 
Several representative, but not limiting, reactions for preparation of a 
Group 4 metal-containing carbosilane dendrimer from a G.sub.n generation 
carbosilane dendrimer and a metallocene substituent-containing reagent are 
as follows. These reactions can be representative of dendrimers formed by 
hydrosilylation/alkenylation methods or cascade methods. For simplicity, 
only one arm of the multiple-armed dendrimer is shown in detail and the 
rest of the dendrimer is represented by .largecircle.. The Roman numerals 
refer generally to a metallocene reagent containing the metallocene 
substituent identified by the same Roman numeral as already given in the 
specification of this patent application. 
##STR33## 
The dendrimers of the present invention can be anchored to a solid phase 
refractory oxide, such as alumina, silica, zirconia and the like, or to an 
insoluble polymer such as cross-linked polystyrene. Such anchored 
dendrimers can be used as anchored homogeneous catalysts. 
The anchored dendrimers can be prepared by growing dendrimers from core 
molecules to a desired generation, G.sub.n, and with some number ,m, 
SiMe.sub.2 H termini at the dendrimer periphery, according to the methods 
already described. However, in the final step of metal-containing reagent 
(such as a metallocene) addition, an insufficient amount of metallocene 
reagent, such as a CH.sub.2 .dbd.CH-containing metallocene as given by 
formulas I-X, is reacted with the SiMe.sub.2 H terminated G.sub.n 
dendrimer. For example, using a twelve-armed G.sub.n dendrimer, only eight 
of the twelve arms can be reacted with the CH.sub.2 .dbd.CH-containing 
metallocene, thus leaving four SiMe.sub.2 H terminated arms remaining. 
Sufficient CH.sub.2 .dbd.CHSi(OEt).sub.3 can then be added in the presence 
of a platinum catalyst to react with the remaining dendrimer SiMe.sub.2 H 
terminated arms. Such a possible reaction sequence is shown schematically 
below. 
##STR34## 
In general, anchored dendrimers include an end group that attaches 
chemically to the solid phase support and the end group is selected based 
on the surface chemistry of the solid phase support. 
The Si(OEt).sub.3 functionalities bind to hydroxyl-containing surfaces, 
such as, for example, those of alumina and silica, to produce an 
immobilized, i.e., anchored dendrimer. FIG. 4 is a schematic illustration 
of anchored dendrimer 30 immobilized on solid phase alumina support 32 at 
support surface 34. Such supported dendrimer catalysts can be used to 
catalyze the gas phase polymerization of olefins. 
Allyltriethoxysilane can be used in place of the vinyltriethoxysilane 
already described to yield an anchoring dendrimer arm 
##STR35## 
where R is an alkyl, methyl or ethyl group. 
Cascade Synthesis Methods 
The following describes certain aspects of the present invention with 
respect to using cascade synthesis methods of forming group 4 
metal-containing organosilicon dendrimers. 
In embodiments which use the cascade synthesis method of the invention, the 
starting monomers can be HSi(CH.dbd.CH.sub.2).sub.3 ; HSi(CH.sub.2 
CH.dbd.CH.sub.2).sub.3 ; HSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3, 
where n=2-20; R(H)Si(CH.dbd.CH.sub.2).sub.2 ; R(H)Si(CH.sub.2 
CH.dbd.CH.sub.2).sub.2 ; or R(H)Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 
].sub.2, where n=2-20, R is a methyl or higher alkyl, phenyl or 
substituted phenyl, halogen, alkoxy, aryloxy or a dialkylamino group. 
The hydrosilylation step of the cascade synthesis can be induced by 
exposing the starting monomers to a catalytic reagent such as, but not 
limited to a transition metal catalyst such as complexes containing Pt, 
Pd, Rh, Ru, Ni, or Ti; organic peroxides; azo compounds; and supported 
transition metal catalysts such as Pt/charcoal, Pt/asbestos, and Raney Ni. 
Alternatively, the hydrosilylation reaction can be induced by exposing the 
starting monomers to ultraviolet radiation or by heating the monomers. The 
hydrosilylation reaction can then be allowed to proceed until 
substantially all of the starting monomers have been consumed. The 
intermediate organosilicon dendrimer produced in the cascade synthesis 
method can further include a dendrimer periphery and, in this embodiment, 
the hydrosilylation reaction can be allowed to proceed until steric 
congestion at the dendrimer periphery causes growth to cease. 
An idealized cascade synthesis scheme is represented pictorially in FIG. 3 
where "M" represents the monomer being added at each stage of the 
synthesis. The growth according to this scheme is not and is not required 
to be regular. Even when all the monomers have been consumed, there will 
still be many unreacted .dbd.CH.sub.2 groups in the as-synthesized 
dendrimer, along with still active catalyst, such as, for example, 
transition metal Pt catalyst. Thus, the dendrimer is a "living polymer", 
i.e., one capable of further growth upon addition of additional monomers 
to yield dendrimers of greater molecular weight. 
After the hydrosilylation step of the cascade synthesis additional monomers 
can be provided and reacted with the intermediate organosilicon dendrimer. 
The additional monomers can have the same chemical composition as the 
starting monomers or, alternatively, have a different chemical composition 
than the starting monomers. Monomers of different chemical composition can 
be monomers such as H(R)Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.2 where 
R is (CH.sub.2).sub.n CH.dbd.CH.sub.2, alkyl, aryl, halogen, alkoxy, 
aryloxy, or dialkylamino and n=0-20. 
In an embodiment of the cascade synthesis, the intermediate organosilicon 
dendrimer can further include a reactive .dbd.CH.sub.2 group or groups 
that can be deactivated in a subsequent step of the synthesis. 
Deactivation of the reactive .dbd.CH.sub.2 group or groups can be 
accomplished by addition of a silicon hydride of composition R.sub.3 SiH 
where R is alkyl, aryl, halogen, alkoxy, aryloxy, siloxy, or dialkylamino 
or mixtures thereof. The silicon hydride can be, but is not limited to, 
Me.sub.2 SiHCl, MeSiHCl.sub.2, HSiCl.sub.3, HSi(OEt).sub.3, 
HSi(OMe).sub.3, HSi(NMe.sub.2).sub.3, PhSiHCl.sub.2 or HSiMe.sub.2 
OSiMe.sub.3. The addition can be catalyzed by a transition metal or other 
catalyst, such as, for example, a Pt catalyst. 
In another embodiment of the cascade synthesis, an intermediate 
organosilicon dendrimer including a reactive CH.dbd.CH.sub.2 group can be 
prepared and reacted with a reagent of the general formula R.sub.2 SiHX 
where R is Me, Et, higher alkyl, or aryl and X is F, Cl, Br, I or alkoxy 
and including a Si--X bond. The thus introduced Si--X bond is then reduced 
to produce a reactive Si--H bond that is then further reacted with the 
Group 4 metal-containing reagent to form the organosilicon dendrimer 
including a Group 4 metal. Reduction of the Si--X bond can be accomplished 
using a reducing agent, such as, for example, LiAlH.sub.4. Reaction with 
the Group 4 metal-containing reagent can be carried out in the presence of 
a catalyst, such as, for example, the Karstedt catalyst, a solution of 
1,3-divinyltetramethyldisiloxane-platinum complex in xylene, 2-3% Pt 
concentration. 
The Group 4 metal-containing reagent can be a metallocene reagent having 
the general formula I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XI(a), 
XI(b) or the following: 
##STR36## 
Alternatively, the Group 4 metal-containing reagent can include a 
metallocene substituent characterized by the formula XI(c), IX(d), XI(e), 
IX(f), XI(g), XI(h), XI(i) or XI(j). 
The intermediate organosilicon dendrimer can contain a .dbd.CH.sub.2 unit 
and the Group 4 metal-containing reagent can then be XII, XIII or XIV. 
The Group 4 metal-containing reagent can also be XV. 
The cascade synthesis method can be used to prepare an anchored dendrimer 
by providing an OH-containing substrate, and carrying out the 
hydrosilylation to produce an intermediate organosilicon dendrimer 
including a reactive CH.dbd.CH.sub.2 group. The step of reacting the 
intermediate organosilicon dendrimer with the Group 4 metal-containing 
reagent further includes adding a reagent of the general formula R.sub.2 
SiHX where R is Me, Et, higher alkyl, or aryl and X is F, Cl, Br, I or 
alkoxy and including a Si--X bond. The Si--X bond is reduced to produce a 
reactive Si--H bond. The reactive Si--H bond is reacted with a deficiency 
of the Group 4 metal-containing reagent further including a vinyl, allyl 
or alkynyl substituent to add to up to 90% of all available 
CH.dbd.CH.sub.2 or CH.dbd.CH groups to produce an intermediate product. 
The intermediate product is subsequently reacted with a vinyl silane or 
allyl silane that includes an SiX.sub.3, substituent where X is OMe, OEt, 
Cl or NMe.sub.2 to produce an anchorable organosilicon dendrimer including 
a Group 4 metal. The vinyl or allyl silane can be, for example, of the 
type CH.sub.2 .dbd.CHSiX.sub.3 or CH.sub.2 .dbd.CHCH.sub.2 SiX.sub.3 where 
X is as already described and can be reacted with up to 30% of the 
originally available CH.dbd.CH.sub.2 or CH.dbd.CH groups. The 
thus-prepared anchorable organosilicon dendrimer including a Group 4 metal 
can be anchored to the OH-containing substrate, such as, for example, by 
reaction with the SiX.sub.3 groups. In the core-based cascade synthesis 
method, the Group 4 metal-containing reagent can include a Si--H bond and 
be chosen from among, but is not limited to, the already-described Group 4 
metal-containing reagents. 
For example, a carbosilane dendrimer can be prepared using a core-based 
cascade synthesis starting with a Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 
].sub.4, n=0-20, core molecule and slowly adding four (4) molar 
equivalents of (CH.sub.2 .dbd.CHCH.sub.2).sub.2 (CH.sub.3)SiH to one of 
Si(CH.dbd.CH.sub.2).sub.4 in the presence of the Karstedt catalyst. A high 
yield of Si[CH.sub.2 CH.sub.2 Si(CH.sub.3)(CH.sub.2 CH.dbd.CH.sub.2).sub.2 
].sub.4 is obtained. Further slow addition of eight (8) molar equivalents 
of (CH.sub.2 .dbd.CHCH.sub.2).sub.2 (CH.sub.3)SiH to this product gave a 
viscous oil dendrimer of molecular weight 2113 as determined by gel 
permeation chromatography (GPC) using a polystyrene standard. 
Starting with such a tetrafunctional core molecule will give a more 
symmetrical dendrimer than when the monomer is used in the absence of such 
a core molecule. However, this dendrimer product will still be less 
regular than a dendrimer grown by the divergent procedure. 
A carbosilane dendrimer can also be grown out from a Si[(CH.sub.2).sub.n 
CH.dbd.CH.sub.2 ].sub.4 core molecule in the presence of the Karstedt 
catalyst to give such a cascade dendrimer. 
In the core-based cascade synthesis method, the intermediate organosilicon 
dendrimer can be reacted with a reagent of the general formula R.sub.2 
SiHX where R is Me, Et, higher alkyl, or aryl and X is F, Cl, Br, I or 
alkoxy and including a Si--X bond. The Si--X bond can be reduced to 
produce a reactive Si--H bond which can be subsequently reacted with the 
Group 4 metal-containing reagent to form the organosilicon dendrimer 
including a Group 4 metal. 
The core-based cascade synthesis method, like the cascade method, can be 
used to produce a Group 4 metal-containing dendrimer anchored to a solid 
phase refractory oxide, such as alumina, silica, zirconia and the like, or 
to an insoluble polymer such as poly(vinyl alcohol). Such anchored 
dendrimers can be used as catalysts, such as, for example, in 
polymerization of olefins. 
In an embodiment of the core-based cascade synthesis, an OH-containing 
substrate is provided and the intermediate organosilicon dendrimer is 
reacted with a reagent such as HSiX.sub.3 or HSiRX.sub.2 where X is Cl, 
Br, I, OMe, OEt, Oalkyl, Oaryl, or NMe.sub.2 and R is Me, Ph, alkyl, or 
aryl to produce an anchorable dendrimer. The anchorable dendrimer can be 
exposed to the OH-containing substrate so that said anchorable dendrimer 
becomes anchored to the substrate. 
In the core-based cascade method for synthesizing a Group 4 transition 
metal-containing organosilicon dendrimer including a desired functionality 
positioned at an internal site on a dendrimer arm, four (4) molar 
equivalents of the first reagent can be used. The reagent reacted with the 
reactive Si--H peripheral dendrimer arm ends can be of the type 
RCH.dbd.CH.sub.2 where R is alkyl, aryl or Me.sub.3 Si. Suitable Group 4 
metal-containing reagents for producing a functionality at an internal 
location on a dendrimer arm have already been described in other 
embodiments of the invention. 
In an embodiment of the core-based method for synthesizing a Group 4 
transition metal-containing organosilicon dendrimer including growing the 
core molecule out to a larger size, four (4) molar equivalents of 
[CH.sub.2 .dbd.CH(CH.sub.2).sub.n ]R.sub.2 SiH where R is methyl or alkyl 
and n=0-20 can be reacted with the core molecule to form an intermediate 
product. The intermediate product subsequently can be reacted with four 
(4) molar equivalents of [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ].sub.2 C.sub.6 
H.sub.5 SiH where n=0-20 to form a second intermediate product. 
Uses of Group 4 Metal-Containing Organosilicon Dendrimers 
The Group 4 metal-containing organosilicon dendrimers of the present 
invention can be used in olefin polymerization or copolymerization methods 
wherein one or more olefin monomers are contacted with the organosilicon 
dendrimer catalyst in solution or in gas phase so that the olefin monomers 
are polymerized or copolymerized to form a polyolefin. 
The monomers can be ethylene and a co-catalyst such as methylalumoxane 
(MAO), B(C.sub.6 F.sub.5).sub.3, a Ph.sub.3 C.sup.+ salt of the(C.sub.6 
F.sub.5).sub.4 B.sup.- anion, or an organic ammonium salt of the (C.sub.6 
Fr3).sub.4 B.sup.- aninon can be provided. Other salts of anions of very 
low nucleophilicity also can be used. 
The monomers can be .alpha.-olefins, such as propylene, 1-butene, styrene, 
and higher .alpha.-olefins, cyclic olefins such as cyclopentene, or 
norbornene, 1,3-dienes such as 1,3-butadiene or isoprene, and a 
co-catalyst such as methylalumoxane (MAO), B(C.sub.6 F.sub.5).sub.3, a 
Ph.sub.3 C.sup.+ salt of the (C.sub.6 F.sub.5).sub.4 B.sup.- anion, or 
an organic ammonium salt of the (C.sub.6 F.sub.5).sub.4 B.sup.- anion can 
be provided. 
The Group 4 metal-containing organosilicon dendrimers of the present 
invention can also be used as catalysts for dehydrogenative condensation 
of silane monomers to form a polysilane as shown in the equation below. 
##STR37## 
The homo- and copolymerizations can be completed at a temperature between 
-60.degree. C. and 120.degree. C., preferably between -10.degree. C. and 
60.degree. C. using aliphatic or cycloaliphatic hydrocarbon solvents such 
as hexane or cyclohexane. More preferably, an aromatic hydrocarbon solvent 
such as toluene is used. Additionally, the polymerization can be done in 
the gas phase. 
The metallocene concentration is in the range of 10.sup.-3 to 10.sup.-8 
mol/ml solvent, preferably in the range of 10.sup.-4 to 10.sup.-6 mol/ml 
solvent. The cocatalyst concentration is in the range of 10.sup.-3 to 
10.sup.-1 mol/ml, preferably in the range of 10.sup.-2 to 10.sup.-1 
mol/ml. 
The desired reactions can be carried out in solution suspension, or bulk, 
using pressures in the range of 0.1 bar to 50 bar, or preferably between 
0.5 bar to 10 bar, whereby the homopolymerizations of cyclic olefins are 
done under normal pressure. 
In order further to illustrate the present invention, the following 
examples are provided. The particular compounds, processes and conditions 
utilized in the examples are meant to be illustrative of the present 
invention and are not limited thereto. 
EXAMPLES 
The following Examples 1-27 are provided to show how metallocene complexes 
and Group 4 metal-containing carbosilane dendrimers were prepared, 
characterized, and used as polymerization catalysts. 
In the examples 1-27, the general dendrimer synthesis procedure as 
described in Seyferth et al., Organometallics, 13 (1994) 2682-2690 was 
followed. Typically, the core molecule was tetravinylsilane, (CH.sub.2 
.dbd.CH).sub.4 Si and successive dendrimer generations were built up from 
this core molecule by successive platinum-catalyzed hydrosilylations of 
all Si--CH.dbd.CH.sub.2 functions with HSiCl.sub.3 or CH.sub.3 SiHCl.sub.2 
and vinylation of the Si--Cl functions thus introduced with vinylmagnesium 
bromide, CH.sub.2 .dbd.CHMgBr, in tetrahydrofuran (THF). The manner 
according to which the final hydrosilylation was accomplished was selected 
according to whether a Si--H function or an unsaturated organic function 
was the desired terminus for the arms of the dendrimer to be reacted with 
the metallocene reagent. To obtain a Si--H terminus, the final 
hydrosilylation was effected with Me.sub.2 SiHCl and the terminal Si--Cl 
bonds were then reduced with LiAlH.sub.4. To obtain a Si--CH.dbd.CH.sub.2 
or Si--CH.sub.2 CH.dbd.CH.sub.2 terminus, the final hydrosilylation was 
effected with Me.sub.2 SiHCl and the terminal Si--Cl bonds were vinylated 
with CH.sub.2 .dbd.CHMgBr or CH.sub.2 .dbd.CHCH.sub.2 MgCl. 
All reactions were carried out under an inert atmosphere, either nitrogen 
or argon. Solvents were purified before use according to methods well 
known to one skilled in the art. The Karstedt catalyst (a solution of 
1,3-divinyltetramethyldisiloxane-platinum complex in xylene, 2-3% Pt 
concentration) was purchased from Aldrich Chemical Co, Milwaukee, Wis. 
Materials used to filter solutions include Florisil.RTM., an activated 
magnesium silicate purchased from Aldrich Chemical Co., and Celite.RTM. 
(Celite 545.RTM.),a diatomaceous earth purchased from Fisher Scientific 
Co. 
The following Examples 1-8 describe preparation of titanocene, zirconocene 
and hafnocene complexes. 
The following Examples 28-41 are provided to show how carbosilane 
dendrimers were prepared, characterized, and used as polymerization 
catalysts using the cascade or core-based synthesis methods of the 
invention. 
In the examples that follow, all reactions were carried out in flame-dried 
glassware in an inert atmosphere such as argon or nitrogen. All solvents 
were dried prior to use, with standard procedures well known to one 
skilled in the art. 
Starting monomers were prepared using standard Grignard vinylation and 
allylation of CH.sub.3 SiHCl.sub.2 and HSiCl.sub.3. The Karstedt catalyst 
solution was purchased from Sigma Aldrich, Milwaukee, Wis. 
Molecular weights were determined in benzene or toluene solution by vapor 
pressure osmometry (VPO). 
Example 1 
Preparation of Me.sub.2 (CH.sub.2 --CH)SiC.sub.5 H.sub.4 (C.sub.5 
H.sub.5)TiCl.sub.2 
A 250 mL Schienk flask equipped with a magnetic stir-bar, a reflux 
condenser and a rubber septum was charged with 60 mL of THF and 3.30 g (22 
mmol) of Me.sub.2 (CH.sub.2 .dbd.CH)SiC.sub.5 H.sub.5. To this solution 
was added at -40.degree. C., slowly by syringe, 13.74 mL of a 1.6 M 
solution of n-BuLi (22 mmol) in hexane. After it had been stirred at room 
temperature for 20 minutes, the resulting solution of Me.sub.2 (CH.sub.2 
.dbd.CH)SiC.sub.5 H.sub.4 Li was cooled to -10.degree. C. and 4.82 g (22 
mmol) of C.sub.5 H.sub.5 TiCl.sub.3 in 30 mL of THF was added slowly. The 
reaction mixture was stirred at room temperature for 12 h and at reflux 
for another 2 h. Subsequently, the volatiles were removed at reduced 
pressure and the residue was dissolved in a mixture of 30 mL of toluene 
and 15 mL of CH.sub.2 Cl.sub.2. The solution was filtered through 
Celite.TM.. The product crystallized when the filtrate was stored at 
-30.degree. C. for 12 h. The product was isolated as purple crystals, 
washed with two 5 mL portions of hexane and dried in vacuum; yield, 5.86 g 
(80%); melting point 145-146.degree. C. Anal. Calcd. for 
C.sub.14,H.sub.18,Cl.sub.2 SiTi:C, 50.47; H, 5.44. Found: C, 51.05; H, 
5.54. The .sup.1 H, .sup.13 C and .sup.29 Si NMR spectra were in agreement 
with the indicated structure. 
Example 2 
Preparation of Me.sub.2 HSiC.sub.5 H.sub.4 (C.sub.5 H.sub.5)TiCl.sub.2 
The same procedure as already described in Example 1 was used to react 2.83 
g (22.8 mmol) of Me.sub.2 HSiC.sub.5 H.sub.5 in 50 mL of THF and an 
equimolar amount of n-BuLi in hexane to generate the lithium 
cyclopentadienide reagent. The lithium cyclopentadienide reagent was then 
reacted with 5.0 g (22.8 nmol) of C.sub.5 H.sub.5 TiCl.sub.3. Once the 
reaction was complete, the solvents were removed at reduced pressure and 
the residue was taken up in benzene and filtered through Celite.TM.. The 
residue obtained on removal of the benzene was recrystallized from 
hexane/toluene. 
Example 3 
Preparation of Me.sub.2 HSiC.sub.5 H.sub.5 (C.sub.5 H.sub.5)TiCl.sub.2 
Substantially the same procedure as described in foregoing Example 1 was 
used to react 6.65 mmol of Me.sub.2 (CH.sub.2 .dbd.CH)SiC.sub.5 H.sub.4 Li 
from 6.65 mmol each of n-BuLi and Me.sub.2 (CH.sub.2 .dbd.CH)SiC.sub.5 
H.sub.5 and 2.2 g (6.65 mmol) of C.sub.5 Me.sub.5 ZrCl.sub.3 in 30 mL of 
THF. After the volatiles were removed at reduced pressure, the residue was 
taken up in 30 mL of toluene. The toluene solution was filtered through 
Celite.TM. and then evaporated in vacuum. The solid residue was washed 
with two 5 mL portions of cold hexane and recrystallized from hexane, 
giving 1.61 g (54%) of white crystals, melting point 121-122.degree. C. 
Anal. Calcd. for C.sub.19 H.sub.28 Cl.sub.2 SiZr: C, 51.08; H, 6.32. 
Found: C, 51.24; H, 6.41. The .sup.1 H, .sup.13 C and .sup.29 Si NMR 
spectra of the product were in agreement with the indicated structure. 
Example 4 
Preparation of Me.sub.2 (CH.dbd.CH)SiC.sub.5 H.sub.5 (C.sub.5 
H.sub.5)ZrCl.sub.2 
The apparatus already described in the foregoing Example 1 was charged with 
10.0 g of ZrCl, and 90 mL of CH.sub.2 Cl.sub.2 to form a solution to which 
was added slowly at 0.degree. C. by syringe 6.4 mL (43 mmol) of dimethyl 
sulfide. The resulting solution was stirred for 30 min and then 5.94 g (43 
mmol) of Me.sub.2 SiC.sub.5 H.sub.5 was added slowly. After the mixture 
was stirred at room temperature for 1 h, the volatiles were removed at 
reduced pressure and the residue was dissolved in 60 mL of THF. To this 
solution 6.70 g (43 mmol) of Me.sub.2 (CH.sub.2 .dbd.CH)SiC.sub.5 H.sub.4 
Li in 50 mL of THF at -20.degree. C. was added. The reaction mixture was 
stirred at room temperature for 12 h and for another 2 h at 50.degree. C., 
then was concentrated to 20 mL. Toluene (40 mL) was added and the solution 
was filtered through Celite.TM.. After removal of most of the solvents at 
reduced pressure, 50 mL of hexane was added. The resulting crystalline 
residue was washed with 5 mL of cold hexane and recrystallized from hexane 
to give 9.4 g (58%) of white crystals, melting point 116-117.degree. C. 
Anal. Calcd. for C.sub.14 H.sub.18 Cl.sub.2 SiZr: C, 44.86; H, 4.82. 
Found: C, 43.74; H 4.91. The .sup.1 H, .sup.13 C and .sup.29 Si NMR 
spectra were in agreement with the indicated structure. 
Example 5 
Preparation of (.mu.-Me(CH.sub.2 .dbd.CH)Si)(C.sub.5 H.sub.4).sub.2 
ZrCl.sub.2 
The same apparatus as already described in Example 1 was charged with 5.0 g 
(25.0 mmol) of Me(CH.sub.2 .dbd.CH)Si(C.sub.5 H.sub.5), and 60 mL of THF 
to form a solution. This solution was cooled to -40.degree. C. and 19.9 mL 
of 2.5 M n-BuLi (49.8 mmol) in hexane was added slowly by syringe. The 
resulting-mixture was stirred for 1 h at room temperature, then cooled to 
-10.degree. C. and 5.81 g (24.9 mmol) of ZrCl.sub.4 was added. The 
reaction mixture was stirred for 48 h at room temperature. Subsequently, 
the THF was removed at reduced pressure, and the residue was taken up in 
100 mL of CH.sub.2 Cl.sub.2. This solution was filtered through 
Celite.TM.. The filtrate was concentrated to 40 mL and stored at 
-30.degree. C. for 12 h. The crystalline solid that formed was washed with 
two 5 mL portions of cold CH.sub.2 Cl.sub.2. and dried in vacuo. The yield 
was 3.3. g (37%) and the melting point was 239-240.degree. C. Anal. Calcd. 
for C.sub.13 H.sub.14 Cl.sub.2 SiZr: C, 43.32; H, 3.91. Found: C, 43.14; H 
3.97. .sup.1 H NMR (CDCl.sub.3): .delta. 0.78 (s, 3H, SiCH.sub.3), 6.0 (m, 
4H, C.sub.5 H.sub.4), 6.26-6.54 (m, 3 H, CH.sub.2 .dbd.CH), 6.92-6.99 (m, 
4H, C.sub.5 H.sub.4). .sup.13 C{.sup.1 H} NMR(CDCl.sub.3): .delta..sub.c 
-6.30 (SiCH.sub.3), 107.89 (C.sub.5 H.sub.4), 114.29 (C.sub.5 H.sub.4), 
115.12 (C.sub.5 H.sub.4), 127.68 (C.sub.5 H.sub.4), 129.51 (C.sub.5 
H.sub.4), 130.19 (CH.sub.2 .dbd.CH), 138.45 (CH.sub.2 .dbd.CH). For NMR 
measurements, Si atoms are numbered from the dendrimer core to the 
dendrimer periphery and that number indicated by a superscript to the 
right of its chemical symbol. 
Example 6 
Preparation of (Me.sub.2 HSi.sub.5 CH.sub.4)(Me.sub.3 SiC.sub.5 
H.sub.4)TiCl.sub.2 
Using the same apparatus as described in the foregoing Example 1, 5.3 mL of 
a solution of 2.5 M n-BuLi in hexane (13.33 mmol) was added to a solution 
of 1.66 g (13.33 mmol) of Me.sub.2 HSiC.sub.5 H.sub.5 in 30 mL of THF. The 
mixture was stirred at room temperature for 20 min. Subsequently, a 
solution of 3.88 g (13.33 mmol) of Me.sub.3 SiC.sub.5 H.sub.4 TiCl.sub.3 
in 20 mL of THF was added slowly at -20.degree. C. The resulting red 
reaction mixture was stirred for 12 h at room temperature. Removal of THF 
at reduced pressure was followed by solution of the residue in benzene and 
filtration through Celite.TM.. Evaporation of the filtrate left a red 
solid that was recrystallized from hexane/toluene to give orange crystals 
(2.8 g, 55%). Anal. Calcd. for C.sub.15 H.sub.24 C.sub.12 SiTi: C, 47.50; 
H, 6.38. Found: C, 47.56; H, 6.55. .sup.1 H NMR (C.sub.6 D.sub.6): .delta. 
0.25-0.40 (m, 15H, SiCH.sub.3), 4.48-4.65 (m, 1 H, SiH), 5.85-6.02 (m, 4H, 
C.sub.5 H.sub.4), 6.38-6.52 (m, 4H, C.sub.5 H.sub.4). For the NMR 
analysis, Si atoms are numbered from the core outward toward the periphery 
of the dendrimer and that number indicated by a superscript to the right 
of its chemical symbol. 
Example 7 
Preparation of (Me.sub.2 (CH.sub.2 .dbd.CH)SiC.sub.5 H.sub.4)(C.sub.5 
H.sub.4)HfCl.sub.2 
A 250 mL schlenk flask equipped with a magnetic stir bar and a rubber 
septum was charged with 50 mL of CH.sub.2 Cl.sub.2 and 8.0 g (25.0 mmol) 
of HfCl.sub.4. To this solution, 3.7 mL (50.0 mmol) of SMe.sub.2 was added 
slowly by syringe at 0.degree. C. After further stirring for 30 min, 8.88 
g (25.0 mmol) of (n-C.sub.4 H.sub.9).sub.3 SnC.sub.5 H.sub.5 was slowly 
added. The resulting mixture was stirred for 12 h at room temperature. The 
solution was concentrated to 20 mL and 30 mL of n-hexane was added. The 
remaining solid was filtered and washed twice with 20 mL of n-hexane. 
Then, the solid was dissolved in 80 mL of THF. After removing the THF at 
reduced pressure, 8.7 g (17.6 mmol) of C.sub.5 H.sub.5 HfCl.sub.3 
(THF).sub.2 remained. 8.5 g (17.2 mmol) of C.sub.5 H.sub.5 HfCl.sub.3 
(THF).sub.2 was dissolved in 60 mL of THF. A solution of 17.2 mmol of 
LiC.sub.5 H.sub.4 SiMe.sub.2 Vi, where "Vi" indicates a vinyl functional 
group, in 50 mL of THF was added at -20.degree. C. The resulting mixture 
was stirred for 15 h at room temperature. All volatiles were removed at 
reduced pressure at room temperature. The residue was dissolved in 80 mL 
of toluene and filtered through Celite.TM.. The solution was concentrated 
to 25 mL and kept for 12 h at -30.degree. C. The crystals obtained were 
filtered at -10.degree. C. and washed with 10 mL of cold toluene. The 
resulting white crystals were dried in vacuum. A yield of 3.83 g (48.0%) 
with melting point 108-110.degree. C. was obtained. Anal. Calcd. for 
C.sub.14 H.sub.18 Cl.sub.2 HfSi: C, 36.26; H, 3.91. Found: C, 34.85; H, 
3.99. .sup.1 H NMR (CDCl.sub.3): .delta. 0.360 (s, 6H, SiCH.sub.3), 
5.700-6.320 (m, 3 CH.sub.2 .dbd.CH) 6.337 (m, 5H, C.sub.5 H.sub.5), 6.443 
(m, 2H, C.sub.5 H.sub.4), 6.621 (m, 2H, C.sub.5 H.sub.4). .sup.13 C 
{.sup.1 H} NMR (CDCl.sub.3): .delta. -2.03 (s, SiCH.sub.3), 114.66 (s, 
C.sub.5 H.sub.5), 116.52 (s, C.sub.5 H.sub.4), 121.30 (s, C.sub.5 
H.sub.4), 124.25 (s, C.sub.5 H.sub.4), 133.02 (s,CH.sub.2 .dbd.CH), 137.97 
(s, CH.sub.2 .dbd.CH). .sup.29 Si {.sup.1 H} NMR (CDCl.sub.3) 
.delta..sub.Si -14.6 (s, Si (C.sub.5 H.sub.4)). For the NMR analysis, Si 
atoms are numbered from the core outward toward the periphery of the 
dendrimer and that number indicated by a superscript to the right of its 
chemical symbol. 
Example 8 
Preparation of (Me.sub.2 (CH.sub.2 .dbd.CHCH.sub.2)SiC.sub.5 
H.sub.4)(C.sub.5 H.sub.4)TiCl.sub.2 
A 250 mL Schlenk flask equipped with a magnetic stir bar and a rubber 
septum was charged with 100 mL of THF and 5.87 g (35.7 mmol) of Me.sub.2 
(CH.sub.2 .dbd.CHCH.sub.2)SiC.sub.5 H.sub.5. To this solution was added at 
-40.degree. C., slowly by syringe, 14.3 mL of a 2.5 M solution of n-BuLi 
(35.7 mmol) in hexane. After it had been stirred at room temperature for 
20 minutes, the resulting solution of Me.sub.2 (CH.sub.2 
.dbd.CHCH.sub.2)SiC.sub.5 H.sub.4 Li was cooled to -10.degree. C. and 7.84 
g (35.7 mmol) of C.sub.5 H.sub.5 TiCl.sub.3 in 60 mL of THF was added 
slowly. The reaction mixture was stirred at room temperature for 12 h. 
Subsequently, the volatiles were removed at reduced pressure and the 
residue was dissolved in 50 mL of CH.sub.2 Cl.sub.2. The solution was 
filtered through Celite.TM. and the CH.sub.2 CL.sub.2 was removed at 
reduced pressure. The crystallized product was washed with 30 ML of 
hexane. The orange crystals were collected and dried in vacuum. A yield of 
11.6 g (93.5%) with melting point 148-149.degree. C. was obtained. The 
.sup.1 H, .sup.13 C and .sup.29 Si NMR spectra were in agreement with the 
indicated structure. 
The following Examples 9-20 describe the synthesis of dendrimers with Group 
4 metallocene termini. 
Example 9 
Preparation of Si[CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 
C.sub.5 H.sub.4 (C.sub.5 Me.sub.5)ZrCl.sub.2 l.sub.4 
A 20 mL Schlenk flask was charged with 0.4024 g (0.9 mmol) of Me.sub.2 
(CH.sub.2 .dbd.CH)SiC.sub.5 H.sub.4 (C.sub.5 Me.sub.5)ZrCl.sub.2, 0.847 g 
(0.225 mmol) of Si (CH.sub.2 CH.sub.2 SiMe.sub.2 H).sub.4, 1 mL of THF and 
20 .mu.L of the Karstedt catalyst solution. The reaction mixture was 
stirred at 50.degree. C. for 12 h. Then, 2 mL of THF were added and the 
solution was filtered through Celite. Volatiles were removed from the 
filtrate at reduced pressure, leaving a light yellow oil that was heated 
at 60 .degree. C. in high vacuum for several hours. A light yellow, waxy 
residue remained, 0.463 g (95%). Anal. Calcd. for C.sub.92 H.sub.156 
Cl.sub.8 Si.sub.9 Zr.sub.4 : C, 51.07; H, 7.27. Found: C, 51.28; H, 7.46. 
.sup.1 H NMR (CDCl.sub.3): .delta. 0.103 (s, 6H, Si.sup.2 CH.sub.3), 
0.20-0.60 (m, 14H,Si.sup.3 CH.sub.3, SiCH.sub.2), 2.00 (s, 15H, C.sub.5 
(CH.sub.3).sub.5), 6.092 (m, 2H, C.sub.5 H.sub.4), 6.432 (m, 2H, C.sub.5 
H.sub.4). .sup.13 C {.sup.1 H) NMR (CDCl.sub.3): .delta..sub.c -4.38 
(Si.sup.2 CH.sub.3), -2.83 (Si.sup.3 CH.sub.3), 2.25 (Si.sup.1 CH.sub.2 
CH.sub.2 Si.sup.2), 6.49 (Si.sup.2 CH.sub.2 CH.sub.2 CH.sub.2 Si.sup.3), 
12.46 (C.sub.5 (CH.sub.3).sub.5), 114.94 (C.sub.5 H.sub.4), 124.13 
(C.sub.5 (CH.sub.3).sub.5, 125.28 (C.sub.5 H.sub.4), 128.75 (C.sub.5 
H.sub.4), .sup.29 Si {.sup.1 H) NMR (CDCl.sub.3): .delta. -3.83 
(Si.sup.3), 5.21 (Si.sup.2 ), 8.77 (Si.sup.1). For the NMR analysis, Si 
atoms are numbered from the core outward toward the periphery of the 
dendrimer and that number indicated by a superscript to the right of its 
chemical symbol. 
Example 10 
Preparation of Si[CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 
C.sub.5 .sub.4 (C.sub.5 H.sub.5)ZrCl.sub.2 l.sub.4 
The same procedure as already set forth in the foregoing Example 7 was used 
in the reaction of 0.5684 g (1.51 mmol) of Me.sub.2 (CH.sub.2 
.dbd.CH)SiC.sub.5 H.sub.4 (C.sub.5 H.sub.5)ZrCl.sub.2 and 0.1423 g (0.377 
mmol) of Si (CH.sub.2 CH.sub.2 SiMe.sub.2 H).sub.4 in 2 mL of THF in the 
presence of 30 .mu.L of the Karstedt catalyst solution. The product (0.710 
g, approximately 100%) was a white solid of melting point 135-136.degree. 
C. Anal. Calcd. for C.sub.72 H.sub.116 Cl.sub.8 Si.sub.9 Zr.sub.4 : C, 
45.93; H, 6.21. Found: C, 45.43; H, 6.39. .sup.1 H NMR (CDCL.sub.3): 
.delta. -0.094 (s, 6H, Si.sup.2 CH.sub.3), 0.20-0.62 (m, 14H, Si.sup.3 
CH.sub.3, SICH.sub.2), 6.43 (s, 5H, C.sub.5 H.sub.5), 6.52 (m, 2H, C.sub.5 
H.sub.4), 6.68 (m, 2H, C.sub.5 H.sub.4). .sup.13 c {.sup.1 H) NMR 
(CDCl.sub.3): .delta. -4.34 (Si.sup.2 CH.sub.3), -2.81 (Si.sup.3 
CH.sub.3), 2.51 (Si.sup.2 CH.sub.2), 6.44 (Si.sup.2 CH.sub.2 CH.sub.2 
Si.sup.3), 6.59 (Si.sup.1 CH.sub.2 CH.sub.2) 8.94 (Si.sub.2 CH.sub.2 
CH.sub.2 Si.sup.3), 115.84 (C.sub.5 H.sub.5) 117.08 (C.sub.5 H.sub.4), 
125.21 (C.sub.5 H.sub.5 125.73 (C.sub.5 H.sub.4) .sup.29 Si {.sup.1 H) NMR 
(CDCl.sub.3): .delta. -3.81 (Si.sup.3), 5.43 (Si.sup.2), 8.79 (Si.sup.1). 
For the NMR analysis, Si atoms are numbered from the core outward toward 
the periphery of the dendrimer and that number indicated by a superscript 
to the right of its chemical symbol. 
Example 11 
Preparation of Si[CH.sub.2 CH.sub.2 SiMe.sub.2 C.sub.2 HCH.sub.2 SiMe.sub.2 
C.sub.5 H.sub.4 (C.sub.5 H.sub.5)TiCl.sub.2 l.sub.4 
The same procedure as already described in the foregoing Example 7 was used 
in the reaction of 0.4987 g (0.0374 mmol) of Si (CH.sub.2 CH.sub.2 
SiMe.sub.2 H).sub.4 in 2 mL of THF in the presence of 40 .mu.L of the 
Karstedt catalyst solution. After the mixture had been stirred at 
50.degree. C. for 4 h, removal of volatiles at reduced pressure left a red 
solid of melting point 118-120.degree. C.; 0.639 g (approximately 100%). 
Anal. Calcd. for C.sub.72 H.sub.116 Cl.sub.8 Si.sub.9 Ti.sub.4 : C, 50.58; 
H, 6.85. Found: C, 50.38; H, 6.82. .sup.1 H NMR (CDCl.sub.3): .delta. 
-0.095 (s, 6H, Si.sup.2 CH.sub.3), 0.20-0.65 (m, 14H, Si.sup.3 CH.sub.3, 
SiCH.sub.2), 6.53 (s, 5H, C.sub.5 H.sub.5), 6.605 (m, 2H, C.sub.5 
H.sub.4), 6.84 (m,2H, C.sub.5 H.sub.4). .sup.13 C (.sup.1 H) NMR 
(CDCl.sub.3): .delta. -4.34 (Si.sup.2 CH.sub.3), 2.72 (Si.sup.3 CH.sup.3), 
2.62 (Si.sup.1 CH.sub.2), 6.64 (Si.sup.2 CH.sub.2 Si.sup.3), 6.70 
(Si.sup.1 CH.sub.2 CCH.sub.2, 8.96 (Si.sup.2 CH.sub.2 CH.sub.2 Si.sup.3), 
120.14 (C.sup.5 H.sup.5), 121.14 (C.sup.5 H.sup.4), 132.02 (C.sup.5 
H.sup.4) .sup.29 Si {.sup.1 H} NMR (CDCl.sup.3): .delta..sub.Si -2.73 
(Si.sup.3), 5.39 (Si.sup.2), 8.84 (Si.sup.1). For the NMR analysis, Si 
atoms are numbered from the core outward toward the periphery of the 
dendrimer and that number indicated by a superscript to the right of its 
chemical symbol. 
Example 12 
Preparation of Si[CH.sub.2 CH.sub.2 SiMe{CH.sub.2 CH.sub.2 SiMe.sub.2 
CH.sub.2 CH.sub.2 SiMe.sub.2 C.sub.5 H.sub.4 (C5H.sub.5)TiCl.sub.2 }.sub.2 
].sub.4 
The same procedure as already described in the foregoing Example 7 was used 
in the reaction of 1.084 g (3.254 mmol) of Me.sub.2 (CH.sub.2 
.dbd.CH)SiC.sub.5 H4(C.sub.5 H.sub.5)TiCl.sub.2 with 0.4109 g (0.407 mmol) 
of Si[CH.sub.2 CH.sub.2 SiMe{CH.sub.2 CH.sub.2 SiMe.sub.2 H).sub.2 ].sub.4 
in 5 mL of THF in the presence of 80 .mu.L of the Karstedt catalyst 
solution. After the reaction mixture had been stirred at 60.degree. C. for 
72 h, it was filtered through Celite.TM.. Removal of volatiles at reduced 
pressure left a red solid of melting point 65-67.degree. C.; 1.34 g 
(9OP6). Anal. Calcd. for C.sub.156 H.sub.260 C.sub.16 Si.sub.21 Ti.sub.8 : 
C, 50.97; H, 7.13. Found: C, 50.83; H, 7.38. .sup.1 H NMR (CDCl.sub.3): 
.delta. -0.100 (s, 12H, Si.sup.3 CH.sub.3), 0.05-0.63 (m, 35H, Si.sup.2 
CH.sub.3, Si.sup.4 CH.sub.3, SiCH.sub.2), 6.54 (m, 10H, C.sub.5 H.sub.5), 
6.60 (m, 4H, C.sub.5 H.sub.4), 6.84 (m, 4H, C.sub.5 H.sub.4). .sup.13 C 
(1H) NMR (CDCl.sub.3): .delta. -6.36 (Si.sup.2 CH.sub.3), -4.24 (Si.sup.3 
CH.sub.3), -2.61 (Si.sup.4 CH3), 2.43 (Si.sup.1 CH.sub.2), 4.52 
(Si.sub..dbd. CH.sub.2,CH.sub.2 Si.sub..dbd.), 4.81 (Si.sup.3 CH.sub.2 
CH.sub.2 Si.sup.2) 6.67 (Si.sup.3 CH.sub.2 CH.sub.2 Si.sup.4), 6.88 
(Si.sup.2 CH.sub.2 CH,Si.sup.3), 9.01 (Si.sup.3 CH.sub.2 CH.sub.2 
Si.sup.4), 120.1 (C.sub.5 H.sub.5), 121.24 (C.sub.5 H.sub.4 (C.sub.5 
H.sub.4)), 128.87 (C.sub.5 H.sub.4), 131.97 (C.sub.5 H.sub.4). .sup.29 Si 
{.sup.1 H) NMR (CDCl.sub.3): .delta. -2.73 (Si.sup.4), 5.41 (Si.sup.3), 
7.44 (Si.sup.2), 8.91 (Si.sup.1). For the NMR analysis, Si atoms are 
numbered from the core outward toward the periphery of the dendrimer and 
that number indicated by a superscript to the right of its chemical 
symbol. 
Example 13 
Preparation of Si[CH.sub.2 CH.sub.2 SiMe.sub.2 {CH.sub.2 CH.sub.2 
SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 C.sub.5 H.sub.4 (C.sub.5 
H.sub.5)ZrCl.sub.2 }.sub.2 ].sub.4 
The same procedure as already described in the foregoing Example 7 was used 
in the reaction of 0.6164 g (1.637 nunol) of Me.sub.2 (CH.sub.2 
.dbd.CH)SiC.sub.5 H.sub.5 (C.sub.5 H.sub.5)ZrCl.sub.2 with 0.2068 g (0.205 
mmol) of Si[CH.sub.2 CH.sub.2 SiMe{CH.sub.2 CH.sub.2 SiMe.sub.2 H}.sub.2 
]H.sub.4 in 1 mL of THF in the presence of 60 .mu.L of the Karstedt 
catalyst solution. After the reaction mixture had been stirred at 
50.degree. C. for 12 h, removal of volatiles at reduced pressure left 
0.823 g (approximately 100%) of a light brown, waxy compound of melting 
point 70-72.degree. C. Anal. Calcd. for C.sub.156 H,.sub.160 Cl.sub.16 
Si.sub.21 Zr.sub.8 : C, 46.58; H, 6.51. Found: C, 46.00; H, 6.36. .sup.1 H 
NMR (CDCl.sub.3): .delta. -0.102 (s, 12H, Si.sup.3 CH.sub.3), 0.08-0.63 
(m, 35H, Si.sup.3 CH.sub.3, Si.sup.4 CH.sub.3, SiCH.sub.2,SiCH.sub.2), 
6.44 (m, 10H, C.sub.5 H.sub.5), 6.53 (m, 4H, C.sub.5 H.sub.4), 6.68 (m, 
2H, C.sub.5 H.sub.4). .sup.13 C (.sup.1 H) NMR (CDCl.sub.3): .delta. -6.53 
(Si.sup.2 CH.sub.3), -4.43 (Si.sup.3 CH.sub.3), -2.88 (Si.sup.4 CH.sub.2), 
2.29 (Si.sup.1 CH.sub.2), 4.29 (Si.sup.2 CH.sub.2 CH.sub.2 Si.sup.3), 4.55 
(Si.sup.1 CH.sub.2 CCH.sub.2 Si.sup.2), 6.38 (Si.sup.3 CH.sub.2 CH.sub.2 
Si.sup.3), 6.63 (Si.sup.2 CH.sub.2 CH.sub.2 Si.sup.3), 8.84 (Si.sup.3 
CH.sub.2 CH.sub.2 Si.sup.4), 115.77 (C.sub.5 H.sub.5), 117.05 (C.sub.5 
H.sub.4), 125.14 (C.sub.5 H.sub.4), 125.69 (C.sub.5 H.sub.4), .sup.29 Si 
{.sup.1 H} NMR (CDCl.sub.3): .delta..sub.Si -3.88 (Si.sup.4), 5.30 
(Si.sup.3), 7.36 (Si.sup.2), 9.02 (Si.sup.1). For the NMR analysis, Si 
atoms are numbered from the core outward toward the periphery of the 
dendrimer and that number indicated by a superscript to the right of its 
chemical symbol. 
Example 14 
Preparation of Si{CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 
Sime(C.sub.5 H.sub.4) ZrCl.sub.2 l.sub.4 
A 50 mL Schlenk flask was charged with 1.11 g (3.09 mmol) of 
(.mu.-Me(CH.sub.2 .dbd.CH)Si)(C.sub.5 H.sub.4).sub.2 ZrCl.sub.2, 0.2911 g 
(0.77 mmol) of Si(CH.sub.2 CH.sub.2 SiMe.sub.2 H).sub.4 in 15 mL of THF 
and 80 gL of the Karstedt catalyst solution. After the reaction mixture 
was stirred at 60.degree. C. for 24 h, removal of volatiles at reduced 
pressure left 1.4 g (approximately 100%) of a white solid (dried at 
50.degree. C. in vacuo) of melting point 86-88.degree. C. Anal. Calcd. for 
C.sub.68 H.sub.100 Cl.sub.8 Zr.sub.4 : C, 44.90; H, 5.54. Found: C, 44.75; 
H, 5.67. .sup.1 H NMR (CDCl.sub.3): .delta. 0.046 (s, 6H, CH.sub.3 
Si.sup.2), 0.25-0.90 (m, 7H, CH.sub.3 Si.sup.3, Si.sup.1 CH.sub.2 CH.sub.2 
Si.sup.2), 1.02-1.35 (m, 4H, Si.sub.2 CH.sub.2 CH.sub.2 Si.sup.3), 
5.90-5.97 (m, 4H, C.sub.5 H.sub.4, 6.94 (m, 4H, C.sub.5 H.sub.4). C 
{.sup.1 H} NMR (CDCl.sub.3): .delta..sub.c -7.68 (Si.sup.3 CH.sub.3), 
-4.34 (Si.sup.2 CH.sub.3), 2.81, 3.36, 5.67, 6.94 (SiCH.sub.2), 108.78 
(C5H.sub.4), 113.90 (C.sub.5 H.sub.4), 115.37 (C.sub.5 H.sub.4), 127.98 
(C.sub.5 H.sub.4), 129.30 (C.sub.5 H.sub.4). For the NMR analysis, Si 
atoms are numbered from the core outward toward the periphery of the 
dendrimer and that number indicated by a superscript to the right of its 
chemical symbol. 
Example 15 
Preparation of Si[CH.sub.2 CH.sub.2 SiMe(CH.sub.2 CH.sub.2 SiMECH.sub.2 
CH.sub.2 SiMe(C.sub.5 H.sub.4).sub.2 ZrCl.sub.2).sub.2 ].sub.4 
A 20 mL Schlenk flask was charged with 450 mg (1.25 mmol) of (Me(CH.sub.2 
.dbd.CH)Si(C.sub.5 H.sub.4).sub.2)ZrCl.sub.2, 158 mg (0.16 mmol) of 
Si(CH.sub.2 CH.sub.2 SiMe(CH.sub.2 CH.sub.2 SiMeH).sub.2).sub.4 in 4 mL of 
THF and 80 .mu.L of the Karstedt catalyst. The reaction mixture was 
stirred at 50.degree. C. for 48 h, and all volatiles were removed at 
reduced pressure. The white solid that remained was dried in vacuum at 
60.degree. C. A yield of 0.60 g (approximately 100%) was obtained. Anal. 
Calcd. for C.sub.148 H.sub.228 Cl.sub.16 Si.sub.21 Zr.sub.8 : C, 45.65; H, 
5.90. Found: C, 45.76; H, 6.15. .sup.1 H NMR (CDCl.sub.3): .delta. -0.15 
(sg, 15H, Si.sup.2 CH.sub.3,Si.sup.3 CH.sub.3), 0.25-0.90 (sg, 18H, 
Si.sup.4 CH.sub.3, SiCH.sub.2), 1.00-1.30 (m, 8H, Si.sup.3 
(CH.sub.2).sub.2 Si.sup.4), 5.95 (m, 8H, C.sub.5 H.sub.4), 6.90 (m, 8H, 
C.sub.5 H.sub.4). .sup.13 C {.sup.1 H) MM (CDCl.sub.3): .delta..sub.c 
-7.78 (s, Si.sup.4 CH.sub.3), -6.43 (s, Si.sup.2 CH.sub.3), -4.37 (s, 
Si.sup.3 CH.sub.3), 2.90, 3.18, 4.47, 5.47, 6.00, 6.74 (s, SiCH.sub.2), 
108.92 (sg, C.sub.5 H.sub.4, 113.68 (m, C.sub.5 H.sub.4, 115.07 (s, 
C.sub.5 H.sub.4), 127.77 (s, C.sub.5 H.sub.4), 128.86 (s, C.sub.5 
H.sub.4). For the NMR analysis, Si are numbered from the core outward 
toward the periphery of the dendrimer and that number indicated by a 
superscript to the right of its chemical symbol. 
Example 16 
Preparation of Si[CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 
(C.sub.5 H.sub.4)(C.sub.5 H.sub.5)HfCl.sub.2 ].sub.4 
A 20 mL Schlenk flask was charged with 1.103 g (2.38 mmol) of 
5-dimethylvinylsilylcyclopentadienyl(cyclopentadienyl)hafnium dichloride, 
224 mg (0.59 nmol) of Si(CH.sub.2 CH.sub.2 SiMe.sub.2 H).sub.4, 2.5 mL of 
THF and 30 gL of the Karstedt catalyst. The reaction mixture was stirred 
at 50.degree. C. for 12 h, and all volatiles were removed at reduced 
pressure. The residue was dissolved in 5 mL of toluene and filtered 
through Florisil.TM.. After the toluene was removed, the remaining light 
brown, waxy compound was dried in vacuum at 50.degree. C. and had melting 
point 73-76.degree. C. and yield 1.21 g (91.29.-). Anal. Calcd. for 
C72H.sub.116 Cl.sub.8 Si.sub.9 Hf.sub.4 : C, 38.74; H, 5.24. Found: C, 
38.83; H, 5.35. .sup.1 H NMR (CDCl.sub.3): .delta. -0.087 (s, 6H, Si.sup.2 
CH.sub.3), 0.23-0.60 (m, 14H, Si.sup.3 CH.sub.3, SiCH.sub.2), 6.337 (s, 
5H, C.sub.5 H4.sub.5), 6.436 (m, 2H, C.sub.5 H.sub.4), 6.594 (m, 2H, 
C.sub.5 H.sub.4). .sup.13 C (.sup.1 H) NMR (CDCl.sub.3): .delta..sub.c 
-4.37 (s, Si.sup.2 CH.sub.3), -2.70 (s, Si.sup.3 CH.sub.3), 2.66 (s, 
Si.sup.1 CH.sub.2 CH.sub.2 Si.sub.2), 6.59 S' Si.sup.2 CH.sub.2 CH.sub.2 
Si.sup.3), 6.74 (s, Si.sup.1 CH.sub.2 CH.sub.2 Si.sup.2), 9.11 (s, 
Si.sup.2 CH.sub.2 CH.sub.2 Si.sup.3), 114.53 (s, C.sub.5 H.sub.5), 115.87 
(s, C.sub.5 H.sub.4) 123.20 (s, C.sub.5 H.sub.4), 124.19 (s, C.sub.5 
H.sub.4). .sup.29 Si {1H) NMR (CDCl.sub.3): .delta. -4.26 (s, Si.sup.3 
(C.sub.5 H.sub.4), 5.00 (s' Si.sup.2 CH.sub.2 CH.sub.2 Si.sup.3), 8.60 (s, 
Si.sup.2 CH.sub.2 CH.sub.2 Si.sup.3). For the NMR analysis, Si atoms are 
numbered from the core outward toward the periphery of the dendrimer and 
that number indicated by a superscript to the right of its chemical 
symbol. 
Example 17 
Preparation of Si{CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 
(C.sub.5 H.sub.4)(C.sub.5 H.sub.5)ZrCl.sub.2).sub.3 ].sub.4 
A 20 mL Schlenk flask was charged with 773 mg (2.05 mmol) of 
5-dimethylvinylsilylcyclopentadienyl(cyclopentadienyl)zirconium 
dichloride, 222 mg (0.17 nimol) of Si(CH.sub.2 CH.sub.2 Si(CH.sub.2 
CH.sub.2 SiMe.sub.2 H)3).sub.4, 3 mL of THF and 80 .mu.L of the Karstedt 
catalyst. The reaction mixture was stirred at 50.degree. C. for 4 h. 
Toluene (5 mL) was added to the reaction mixture and the resulting 
solution was then filtered through Celite.TM.. All volatiles were removed 
at reduced pressure. A light brown oil remained and was dried at 
50.degree. C. in high vacuum with yield 0.90 g (90%). Anal. Calcd. for 
C.sub.224 H.sub.364 Cl.sub.24 Si.sub.29 Zr.sub.12 : C, 46.25; H, 6.31. 
Found: C, 46.53; H, 6.11. .sup.1 H NMR (CDCl.sub.3): .delta. -0.113 (s, 
18H, Si.sup.3 CH.sub.3), 0.10-0.40 (m, s(overlapped), 42H, Si.sup.4 
CH.sub.3, Si.sup.2 CH.sub.2 CH.sub.2 Si.sup.3, Si.sup.3 CH.sub.2 CH.sub.2 
Si.sup.4), 0.47-0.60 (m, 4H, Si.sup.1 CH.sub.2 CH.sub.2 Si.sup.2), 6.44 
(s, 15H, C.sub.5 H.sub.5), 6.3 (m, 6 H, C.sub.5 H.sub.4), 6.68 (m, 6H, 
C.sub.5 H.sub.4). .sup.13 C {.sup.1 H} NMR (CDCL.sub.3): .delta..sub.c 
-4.31 (S, Si.sup.3 CH.sub.3), -2.78 (S, Si.sup.4 CH3), 2.34 (s(overlapped, 
broad), Si.sup.1 CH.sub.2, Si.sup.2 CH.sub.2), 6.33 (s, Si.sup.3 CH.sub.2 
CH.sub.2 Si.sup.4), 6.77 (s, Si.sup.2 CH.sub.2 CH.sub.2 Si.sup.3), 8.91 
(s, Si.sup.3 CH.sub.2 CH.sub.2 Si.sup.4), 115.83 (s, C.sub.5 H.sub.5), 
117.01 (s, C.sub.5 H.sub.4), 125.16 (s, C.sub.5 H.sub.4), 125.73 (s, 
C.sub.5 H.sub.4). .sup.29 Si {1H) NMR (CDCl.sub.3): .delta..sub.Si -4.21 
(S, Si.sup.4 C.sub.5 H.sub.5), 4.95 (s, Si.sup.3), 8.66 (s(overlapped), 
Si.sup.1,Si.sup.2). For the NMR analysis, Si atoms are numbered from the 
core outward toward the periphery of the dendrimer and that number 
indicated by a superscript to the right of its chemical symbol. 
Example 18 
Preparation of Si[CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 
(C.sub.5 H.sub.4)(Me.sub.3 SiC.sub.5 H.sub.4)RiCl.sub.2 ].sub.4 
The following example is provided to demonstrate the coupling of a 
metallocene-containing compound with a Si--H bond and a dendrimer with 
vinyl groups at its termini to produce the desired metallocene-containing 
dendrimer. 
A 20 mL Schlenk flask was charged with 532 mg (1.40 mmol) of 
5-dimethylhydrogensilylcyclopentadienyl(trimethylsilylcyclopentadienyl)tit 
anium dichloride, 168.0 mg (0.35 Tmnol) of Si(CH.sub.2 CH.sub.2 SiMe.sub.2 
Vi).sub.4, where Vi represents a vinyl functional group, 2.5 mL of THF and 
70 .mu.L of the Karstedt catalyst. The reaction mixture was stirred at 
50.degree. C. for 4 h, and volatiles were removed at reduced pressure. The 
red solid that remained was dried in high vacuum, as previously defined, 
at 60.degree. C. and had a yield of approximately 70% in relation to the 
reacted vinyl groups of the dendrimer. .sup.1 H NMR (CDCl.sub.3): .delta. 
0.10-0.60 (m, s(overlapped), 20H, SiCH.sub.3, SiCH.sub.2), 5.60-6.20 (m, 
.about.1H, CH.dbd.CH.sub.2), 6.50-6.90 (m, 8H, C.sub.5 H.sub.4). For the 
NMR analysis, Si, atoms are numbered from the core outward toward the 
periphery of the dendrimer and that number indicated by a superscript to 
the right of its chemical symbol. 
The following Examples 19 and 20 describe preparation of dendrimers 
suitable for anchoring to a solid phase, such as a refractory oxide. 
Example 19 
Preparation of Si(CH.sub.2 CH.sub.2 SiMe.sub.2).sub.4 (CH.sub.2 CH.sub.2 
SiMe.sub.2 (C.sub.5 H4)(C.sub.5 H.sub.5)TiCl.sub.2).sub.2.5 (CH.sub.2 
CH.sub.2 Si(OMe).sub.3).sub.1.5 
A 20 mL Schlenk flask was charged with 714 mg (2.14 mmol) of 
5-dimethylvinylsilylcyclopentadienyl(cyclopentadienyl)titanium dichloride, 
323 mg (0.86 mmol) of Si(CH.sub.2 CH.sub.2 SiMe.sub.2 H).sub.4, 3 mL of 
THF and 60 gL of the Karstedt catalyst. The reaction mixture was stirred 
at 40.degree. C. for 0.5 h. and 190 mg (1.285 mmol) of 
vinyltrimethoxysilane was added to the reaction mixture. The resulting 
reaction mixture was then stirred at 40.degree. C. for 8 h. All volatiles 
were removed at reduced pressure. A red, waxy compound remained and had 
yield 1.22 g (approximately 100%). 15 Anal. Calcd. for C.sub.58.5 
H.sub.107 Cl.sub.504.5 Si.sub.9 Ti.sub.2.5 : C, 49.06; H, 7.53. Found: C, 
48.51; H, 7.28. .sup.1 H NMR (CDCl.sub.3): .delta. -0.10--0.07 
(s(overlapped), 24H, Si.sup.2 CH.sub.3), 0.22-0.63 (m, 47H, Si.sup.3.1 
CH.sub.3, SiCH.sub.2,), 3.552 (s, 13.5H, OCH.sub.3), 6.530 (s, 12.5H, 
C.sub.5 H.sub.5), 6.600 (m, 5H, C.sub.5 H.sub.4), 6.838 (m, 5H, C.sub.5 
H.sub.4). .sup.13 C {.sup.1 H) NMR (CDCl.sub.3): .delta..sub.c -4.73 (Sg, 
Si.sup.2 CH.sub.3), -2.90 (Sg, Si.sup.3 CH.sub.3), 0.98 (s, Si.sup.2 
CH.sub.2 CH.sub.2 Si(OMe).sub.3), 2.28 (s, Si.sup.1 CH.sub.2 CH.sub.2 
Si.sup.2), 5.19 (s, Si.sup.2 CH.sub.2 CH.sub.2 Si(OMe).sub.3), 6.33 (sg, 
Si.sup.1 CH.sub.2 CH.sub.2 Si.sup.2, Si.sup.2 CH.sub.2 CH.sub.2 SiC.sub.5 
H.sub.5), 8.67 (s, Si.sup.2 CH.sub.2 CH.sub.2 SiC.sub.5 H.sub.5), 50.5 
(sg, OCH.sub.3), 120.3 (sg, C.sub.5 H.sub.4,C.sub.5 H.sub.5), 128.8-131.8 
(sg, C.sub.5 H.sub.4), where "sg" denotes a group of signals and "Me" 
denotes a methyl group. For the NMR analysis, Si atoms are numbered from 
the core outward toward the periphery of the dendrimer and that number 
indicated by a superscript to the right of its chemical symbol. 
Example 20 
Preparation of Si(CH.sub.2 CH.sub.2 SiMe.sub.2).sub.4 (CH.sub.2 CH.sub.2 
SiMe.sub.2 (C.sub.5 H.sub.4)(C.sub.5 H.sub.5)ZrCl.sub.2).sub.2.5 (CH.sub.2 
CH.sub.2 Si(OMe).sub.3).sub.1.5 
A 20 mL Schienk flask was charged with 542 mg (1.44 mmol) of 
5-dimethylvinylsilylcyclopentadienyl(cyclopentadienyl)zirconium 
dichloride, 217 mg (0.58 nunol) of Si(CH.sub.2 CH.sub.2 SiMe.sub.2 
H).sub.4, 2 mL of THF and 60 .mu.L of the Karstedt catalyst. The reaction 
mixture was stirred at 40.degree. C. for 0.5 h. and then 128 mg (0.86 
mmol) of vinyltrimethoxysilane was added to the mixture. The resulting 
reaction mixture was stirred at 40.degree. C. for 8 h. All volatiles were 
removed at reduced pressure. The residue was dissolved in methylene 
chloride and filtered through silica gel. After all volatiles were 
removed, a light brown, waxy compound remained. A yield of 842 mg (95%) 
was obtained. Anal. .sup.1 H NMR (CDCl.sub.3): .delta. 0.10-0.10 (s 
(overlapped), 24H, Si.sup.2 CH.sub.3), 0.22-0.63 (m, 47H, Si.sup.3.1 
CH.sub.3, SiCH.sub.2), 3.56 (s, 13.5H, OCH.sub.3), 6.43 (s, 12.5H, C.sup.5 
H.sub.5), 6.52 (m, 5H, C.sub.5 H.sub.4), 6.68 (m, 5H, C.sub.5 H.sub.4). 
For the NMR analysis, Si atoms are numbered from the core outward toward 
the periphery of the dendrimer and that number indicated by a superscript 
to the right of its chemical symbol. 
The following Examples 21 and 22 demonstrate the use of dendrimers with 
Group 4 metallocene termini as catalysts. 
Example 21 
Polymerization of Phenylsilane Induced by Si[CH.sub.2 CH.sub.2 SiMe.sub.2 
CH.sub.2 CH.sub.2 SiMe.sub.2 (C.sub.5 H.sub.4)(C.sub.5 H.sub.5)ZrCl.sub.2 
].sub.4 
A 25 mL Schlenk flask equipped with a rubber septum was charged with a stir 
bar, 127 mg (67.4 mmol) of Si(CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 
CH.sub.2 SiMe.sub.2 (C.sub.5 H.sub.4)(C.sub.5 H.sub.4)ZrCl.sub.2 ].sub.4 
and 4 mL of toluene. The mixture was cooled to -10.degree. C. and 0.21 mL 
(0.53 mmol) of a 2.5 m solution of n-butyllithium in hexane was injected 
by syringe. After stirring for 5 min at 0.degree. C., 2.0 g (18.5 mmol) of 
phenylsilane, PhSiH.sub.3, was injected into the flask, forming a light 
yellow, clear solution. Vigorous bubbling occurred immediately upon 
introduction of the phenylsilane. After removal of the ice bath, and 
within 15 min of being exposed to room temperature, the reaction mixture 
became red. After stirring for 1 h at room temperature, 4 mL of n-hexane 
was added and the reaction mixture was filtered through Celite.TM.. Then, 
all volatiles were removed at reduced pressure leaving a yellow, waxy 
compound that was dried in vacuum with yield 1.820 g (91.6%). 
Spectroscopic evidence, including NMR and infrared (IR) spectroscopic 
data, showed the compound to be a poly(phenylsilane). Anal. Calcd. for 
H(PhSiH).sub.x H: C, 67.8; H, 5.7. Found: C, 67.2; H, 5.8. .sup.1 H NMR 
(CD.sub.2 Cl.sub.2): .delta. 3.65-5.10 (m (broad), 1H, SiH), 6.50-7.50 (m 
(broad), 5.8H, C.sub.6 H.sub.5). IR 3065 cm.sup.-1 (C--H), 2106 cm.sup.-1 
(Si--H). 
Example 22 
Polymerization of Phenylsilane Induced by Si[CH.sub.2 CH.sub.2 
SiMe(CH.sub.2 CH.sub.2 SiMe.sub.2 (C.sub.5 H.sub.4)(CH.sub.5 
H.sub.5)ZrCl.sub.2).sub.2 ].sub.4 
A 25 mL Schlenk flask equipped with a rubber septum was charged with a stir 
bar, 146 mg (36.3 .mu.mol) of Si[CH.sub.2 CH.sub.2 SiMe (CH,CH.sub.2 
SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 (C.sub.5 H.sub.4)(C.sub.5 
H.sub.5)ZrCl.sub.2).sub.2 ].sub.4 and 4 mL of toluene. The mixture was 
cooled to -10.degree. C. and 0.23 mL (0.57 mmol) of a 2.5 m solution of 
n-butyllithium in hexane was injected by syringe. After stirring for 7 min 
at -10.degree. C., 2.1 g (19.4 mmol) of phenylsilane, was injected into 
the flask, forming a light yellow, clear solution. Vigorous bubbling 
occurred immediately upon introduction of the phenylsilane. After 10 min, 
the ice bath was removed, and within 10 min of being exposed to room 
temperature, the reaction mixture became red. After stirring for 50 min at 
room temperature, 4 mL of n-hexane was added and the reaction mixture was 
filtered through Celite.TM.. Then, all volatiles were removed at reduced 
pressure leaving an orange, waxy compound that was dried in vacuum with 
yield 1.95 g (95%). Spectroscopic evidence, including NMR and infrared 
(IR) spectroscopic data, showed the 20 compound to be a 
poly(phenylsilane). Anal. Calcd. for H(PhSiH).sub.x H: C, 67.8; H, 5.7. 
Found: C, 67.7; H, 5.8. .sup.1 H NMR ((CD.sub.3).sub.2 CO): .delta. 
3.70-5.30 (m (broad), 1H, SiH), 6.60-7.85 (m (broad), 5.2H, C.sub.6 
H.sub.5). IR 3065 cm.sup.-1 (C--H), 2106 cm.sup.-1 (Si--H) 
The following Examples 23-27 are provided to demonstrate the use of the 
catalysts of the invention for catalysis of olefin polymerization. 
Example 23 
Homopolymerization of Ethylene 
A 250 ml four-necked flask equipped with reflux condenser, magnetic stir 
bar, inside thermometer, nitrogen inlet/outlet and a gas inlet tube was 
filled with 100 ml toluene, 0.66 ml MAO solution (10% by weight in 
toluene) and 0.5 ml of a 0.002 M solution of (Si[CH.sub.2 CH.sub.2 
SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 C.sub.5 H.sub.4 (C.sub.5 
H.sub.5)ZrCl.sub.2 ].sub.4), described in Example 10, in toluene. This 
solution was stirred for 20 minutes to activate the catalyst The catalyst 
solution was then heated to 40.degree. C. and held at this temperature. 
Ethylene was bubbled through the system for 15 minutes. The reaction was 
stopped by addition of a 50 ml methanol solution containing 0.5 ml 1 N 
HCl. The polymer was then filtered and washed several times with methanol. 
Finally, the polymer was dried in vacuum at 50.degree. C. for 20 hours 
yielding 1.44 g polyethylene, which translates to a catalyst activity of 
5760 kg/mol-hour. 
Example 24 
Copolymerization of Ethylene with Prolpylene 
The polymerization was done as described for Example 23 using 5 ml of 0.002 
M solution of (Si[CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 
SiMe.sub.2 C.sub.5 H.sub.4 (C.sub.5 H.sub.5)ZrCl.sub.2 ].sub.4), described 
in Example 10, and bubbling a mixture of ethylene/propylene (1:1 by 
volume), through the system. The polymerization was done at 20.degree. C. 
for 60 minutes providing 14.6 g of a sticky copolymer, which translates to 
a catalyst activity of 1460 kg/mol-hour. 
Example 25 
Homopolymerization of Cyclopentene 
A 250 ml two-necked flask equipped with septa, magnetic stir bar, nitrogen 
inlet and outlet was filled in an inert atmosphere box with 6.5 mg of 
(Si{CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe(C.sub.5 
H.sub.4).sub.2 ZrCl.sub.2 ].sub.4), described in Example 14. The catalyst 
was then dissolved in -20 ml MAO solution. The flask was transferred out 
of the inert atmosphere box and the homogeneous solution was stirred for 
0.5 hours to activate the catalyst. 
In a separate Schlenk tube, which was flame dried under nitrogen flow, 30 
ml cyclopentene and 10 ml MAO solution were mixed. This solution was 
transferred in an air tight syringe to the preactivated 
catalyst/cocatalyst solution. The thus-obtained solution was then stirred 
for 24 hours at 25.degree. C. After this time period, a solution of 50 ml 
ethanol containing 20% 1 N HCl was carefully added. The solution was then 
stirred for 5 hours to remove cocatalyst residues. The white polymer was 
filtered and washed several times with methanol and then acetone. The 
polymer was then dried for 24 hours in a vacuum oven at 80.degree. C., 
yielding 2.5 g of a white crystalline polymer which is insoluble in common 
solvents at room temperature. The catalyst activity is 29 kg/mol-hour. 
Differential scanning calorimetry (DSC) shows no melting point before 
decomposition of the material. 
Example 26 
Homopolymerization of 1-Hexene 
A 250 ml two-necked flask equipped with septa, magnetic stir bar, nitrogen 
inlet and outlet was filled in an inert atmosphere box with 4.0 mg of 
(Si[CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe(C.sub.3 
H.sub.4).sub.2 ZrCl.sub.2 ].sub.4), described in Example 14. The catalyst 
was then dissolved in -20 ml MAO solution. The flask was transferred out 
of the inert atmosphere box and the homogeneous solution was stirred for 
0.5 hours to activate the catalyst. 
In a separate Schlenk-tube, which was flame dried under nitrogen flow, 20 
ml 1-hexene and 10 ml MAO solution were mixed. This solution was 
transferred in an air tight syringe to the preactivated 
catalyst/cocatalyst solution. The obtained solution was then stirred for 7 
days at 25.degree. C. The polymerization was stopped by addition of 50 ml 
of ethanol. The obtained cocatalyst residues were filtered. The remaining 
solution was concentrated at the rotavap leading to a clear, low 
viscosity, atactic polyhexene, which was dried in vacuum at 60.degree. C. 
for 24 hours. The yield was 4.1 g, which translates 20 to a catalyst 
activity of 11 kg/mol-hour. 
Example 27 
Copolymerization of 1-Hexene with Cyclopentene 
A 250 ml two-necked flask equipped with septa, magnetic stir bar, and 
nitrogen inlet and outlet was filled in an inert atmosphere box with 4.0 
mg of (Si(CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe(C.sub.5 
H.sub.5).sub.2 ZrCl.sub.2 ].sub.4), described in Example 14. The catalyst 
was then dissolved in 20 ml MAO solution. The flask was transferred out of 
the inert atmosphere box and the homogeneous solution was stirred for 0.5 
hours to activate the catalyst. 
In a separate Schlenk-tube, which was flame dried under nitrogen flow, 10 
ml 1-hexene, 10 ml cyclopentene and 10 ml MAO solution were mixed. This 
solution was transferred in an air tight syringe to the preactivated 
catalyst/cocatalyst solution. The thus-obtained solution was then stirred 
for 4 days at 25.degree. C. After this time period, a solution of 50 ml 
ethanol containing 20% 1 N HCl was carefully added and stirred for 5 hours 
to remove cocatalyst residues. The polymer was filtered and washed several 
times with methanol and acetone. The polymer was then dried for 24 hours 
in a vacuum oven at 80.degree. C., yielding 3.2 g of a white, wax-type 
polymer, which translates to a catalyst activity of 15 kg/mol-hour. 
Example 28 
The following example describes preparation of a cascade dendrimer from 
(CH.sub.2 .dbd.CH).sub.2 MeSiH in THF at low concentration. 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 372 
mg (3.79 mmol) of (CH.sub.2 .dbd.CH).sub.2 MeSiH and 3 mL of THF. Then, 1 
drop of the Karstedt catalyst was added. The resulting mixture was stirred 
at room temperature for 24 hours. The volatiles were removed at reduced 
pressure at room temperature. A colorless oil remained. A yield of 371 mg, 
approximately 100%, was obtained. Anal. Calcd. for (C.sub.5 H.sub.10 
Si).sub.n : C, 61.14; H, 10.26. Found: C, 60.91; H, 10.23. .sup.1 H NMR 
(C.sub.6 D.sub.6): .delta. -0.05-0.45 (s(overlapped), 3H, SiCH.sub.3) 
0.50-1.28 (m, 4H, SiCH.sub.2), 5.60-6.40 (m, 3H, CH.dbd.CH.sub.2). 
Example 29 
The following example describes preparation of a cascade dendrimer from 
(CH.sub.2 .dbd.CH).sub.2 MeSiH in THF at high concentration. 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 375 
mg (3.82 mmol) of (CH.sub.2 .dbd.CH).sub.2 MeSiH and 0.5 mL of THF. Then, 
1 drop of the Karstedt catalyst was added. The reaction started 
spontaneously and the temperature increased to approximately 50.degree. C. 
The resulting mixture was kept at approximately 50.degree. C. and stirred 
for 2 hours. The volatiles were removed at reduced pressure at room 
temperature. A colorless oil remained. A yield of 375 mg, approximately 
100%, was obtained. Anal. Calcd. for (C.sub.5 H.sub.10 Si).sub.n : C, 
61.14; H, 10.26. Found: C, 60.95; H, 10.25. .sup.1 H NMR (C.sub.6 
D.sub.6): .delta. -0.05-0.35 (s(overlapped), 3H, SiCH.sub.3), 0.50-1.28 
(m, 4H, SiCH.sub.2), 5.63-6.40 (m, 3H, CH.dbd.CH.sub.2). Molecular Weight 
(VPO in benzene): M=738 g/mol. 
Example 30 
The following example describes preparation of a cascade dendrimer from 
(CH.sub.2 .dbd.CH).sub.2 MeSiH in Et.sub.2 O. 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 750 
mg (7.64 mmol) of (CH.sub.2 .dbd.CH).sub.2 MeSiH and 0.5 mL of ether. This 
mixture was stirred in a bath at room temperature. Then, 1 drop of the 
Karstedt catalyst was added. An exothermic reaction started. The mixture 
was stirred at 35.degree. C. for 2 hours. The volatiles were removed at 
reduced pressure at room temperature. A colorless oil remained. A yield of 
749 mg, approximately 100%, was obtained. Anal. Calcd. for (C.sub.5 
H.sub.10 Si).sub.n : C, 61.14; H, 10.26. Found: C, 60.97; H, 10.28. .sup.1 
H NMR (C.sub.6 D.sub.6): .delta. -0.5-0.40 (s(overlapped), 3H, 
SiCH.sub.3), 0.45-1.28 (m, 4H, SiCH.sub.2), 5.63-6.40 (m, 3H, 
CH.dbd.CH.sub.2). Molecular Weight (calculated from VPO obtained in 
Example 5): M=558 g/mol. 
Example 31 
The following example describes stepwise growth of a cascade dendrimer from 
(CH.sub.2 .dbd.CH).sub.2 MeSiH in Et.sub.2 O including steps 31A, 31B, and 
31C. 
Step 31A 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 750 
mg (7.64 mmol) of (CH.sub.2 .dbd.CH).sub.2 MeSiH and 0.5 mL of ether. This 
mixture was stirred in a bath at room temperature. Then, 1 drop of the 
Karstedt catalyst was added. An exothermic reaction started. The mixture 
was stirred at 35.degree. C. for 4 hours. The ether was removed at reduced 
pressure at room temperature. A colorless oil ("Product 31A") remained. A 
yield of 750 mg, approximately 100%, was obtained. .sup.1 H NMR (C.sub.6 
D.sub.6): .delta. -0.05-0.45 (s(overlapped), 3H, SiCHH.sub.3), 0.50-1.25 
(m, 4H, SiCH.sub.2), 5.63-6.38 (m, 3H, CH.dbd.CH.sub.2). Molecular Weight 
(VPO in toluene): M=526 g/mol. 
Step 31B 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 500 
mg of Product 31A dendrimer prepared in the foregoing Step 31A. This 
mixture was stirred in a bath at 40.degree. C. One drop of the Karstedt 
catalyst was added and, then, over a 4 hour period, was added 500 mg (5.09 
mmol) of (CH.sub.2 .dbd.CH).sub.2 MeSiH by syringe. The reaction mixture 
turned light yellow. This mixture was kept at 50.degree. C. for another 2 
hours. The volatiles were removed at reduced pressure at room temperature. 
A colorless, viscous oil ("Product 4B") remained. A yield of 1.0 g, 
approximately 100%, was obtained. Anal. Calcd. for (C.sub.5 H.sub.10 
Si).sub.n : C, 61.14; H, 10.26. Found: C, 61.61; H, 10.45. .sup.1 H NMR 
(C.sub.6 D.sub.6): .delta. -0.05-0.45 (s(overlapped), 3H, SiCH.sub.3), 
0.50-1.30 (m, 4H, SiCH.sub.2), 5.63-6.42 (m, 3H, CH.dbd.CH.sub.2) 
Molecular Weight (VPO in toluene): M=831 g/mol. 
Step 31C 
Using the same procedure and reagent quantities as described above in Step 
31B, but substituting Product 31B for Product 31A, a third reaction was 
carried out. A colorless oil, ("Product 31C"), more viscous than Product 
31B remained. A yield of 1.0 g, approximately 100%, was obtained. Anal. 
Calcd. for (C.sub.5 H.sub.10 Si).sub.n : C, 61.14; H, 10.26. Found: C, 
61.56; H, 10.28. .sup.1 H NMR (C.sub.6 D.sub.6): .delta. -0.05-0.45 
(s(overlapped), 3H, SiCH.sub.3), 0.50-1.35 (m, 4H, SiCH.sub.2), 5.62-6.42 
(m, 3H, CH.dbd.CH.sub.2). .sup.13 C NMR {.sup.1 H}, (CDCl.sub.3): .delta. 
-7.00 to -3.00 (SiCH.sub.3), 1.0-11.0 (SiCH.sub.2), 131.0-133 
(SiCH.dbd.--CH.sub.2), 136.0-140 (SiCH.dbd.CH.sub.2). .sup.29 Si NMR 
{.sup.1 H}, (CDCl.sub.3): .delta..sub.Si -11.4 to -10.3 
(Si(CH.dbd.CH.sub.2).sub.2), -1.70-0.70 (SiCH.dbd.CH.sub.2) 7.80-8.70 
(SiCH.sub.2 CH.sub.2 Si) Molecular Weight (VPO in toluene): M=886 g/mol. 
Example 32 
The following example describes preparation of a cascade dendrimer from 
(CH.sub.2 .dbd.CH).sub.3 SiH in Et.sub.2 O. 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 1 
mL of ether and 1 drop of the Karstedt catalyst. This mixture was stirred 
in a bath at 35.degree. C. Then, over a 5 minute period 722 mg (7.00 mmol) 
of (CH.sub.2 .dbd.CH).sub.3 SiH was added slowly by syringe. The mixture 
was stirred at 35.degree. C. for 6 hours. The volatiles were removed at 
reduced pressure at room temperature. A colorless, somewhat viscous oil 
remained. A yield of 770 mg, approximately 100%, was obtained. Anal. 
Calcd. for (C.sub.6 H.sub.10 Si).sub.n : C, 65.38; H, 9.14. Found: C, 
65.30; H, 9.24. .sup.1 H NMR (C.sub.6 D.sub.6): .delta. -0.10-1.40 (m, 
approx. 2.7H, SiCH.sub.2), 5.67-6.50 (m, 3H, CH.dbd.CH.sub.2). .sup.13 C 
NMR {.sup.1 H}, (CDCl.sub.3): .delta..sub.c -1.0-10.5 (SiCH.sub.3), 
132.0-137.5 (SiCH.dbd.CH.sub.2). .sup.29 Si NMR {.sup.1 H}, (CDCl.sub.3): 
.delta..sub.Si -18.3 to -14.9 (Si(CH.dbd.CH.sub.2).sub.3), -9.1 to -3.7 
(Si(CH.dbd.CH.sub.2).sub.2), 0.4-5.0 (SiCH.dbd.CH.sub.2), 10.3-11.4 
(SiCH.sub.2) Molecular Weight (VPO in toluene): M=531 g/mol. 
Example 33 
The following example describes preparation of a cascade dendrimer from 
(CH.sub.2 .dbd.CHCH.sub.2).sub.2 MeSiH in Et.sub.2 O. 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 813 
mg (6.44 mmol) of (CH.sub.2 .dbd.CHCH.sub.2).sub.2 MeSiH and 0.5 mL of 
ether. This mixture was stirred at room temperature. Then, 1 drop of the 
Karstedt catalyst was added. The reaction started spontaneously and the 
temperature increased. The mixture was stirred at 35.degree. C. for 3 
hours. The volatiles were removed at reduced pressure at room temperature. 
A colorless, highly viscous oil remained. A yield of 812 mg, approximately 
100%, was obtained. Anal. Calcd. for (C.sub.7 H.sub.14 Si).sub.n : C, 
66.58; H, 11.18. Found: C, 66.52; H, 11.12. .sup.1 H NMR(C.sub.6 D.sub.6): 
.delta.0.00-0.30 (s(overlapped), 3H, SiCH.sub.3), 0.60-0.93 (m, 4H, 
SiCH.sub.2 CH.sub.2 CHhd 2Si), 1.38-1.85 (m, 4H, SiCH.sub.2 
CH.dbd.CH.sub.2, SiCH.sub.2 CH.sub.2 CH.sub.2 Si), 4.90-5.13 (m, 2H, 
CH.sub.2 CH.dbd.CH.sub.2), 5.70-6.02 (m, 1H, CH.sub.2 CH.dbd.CH.sub.2). 
.sup.13 C NMR {.sup.1 H}, (CDCl.sub.3): .delta..sub.c -6.00 to -4.50 
(SiCH.sub.3), 17.5-19.5 (SiCH.sub.2), 21.0-23.0 (SiCH.sub.2 CH.sub.2 
CH.sub.2 Si), 113.0 (SiCH.sub.2 CH.dbd.CH.sub.2), 134.0 (SiCH.sub.2 
CH.dbd.CH.sub.2). .sup.29 Si NMR {.sup.1 H}, (CDCl.sub.3): .delta..sub.Si 
-1.0-1.5 (SiCH.sub.2 CH.sub.2, SiCH.sub.2 CH.dbd.CH.sub.2). Molecular 
Weight (VPO in benzene): M=3668 g/mol. 
Example 34 
The following example describes preparation of a cascade dendrimer from 
(CH.sub.2 .dbd.CHCH.sub.2).sub.3 SiH in Et.sub.2 O. 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 1 
mL of ether and 1 drop of the Karstedt catalyst. This mixture was stirred 
in a bath at 35.degree. C. Then, over a 5 minute period 841 mg (5.52 mmol) 
of (CH.sub.2 .dbd.CHCH.sub.2).sub.3 SiH was added slowly by syringe. The 
mixture was stirred at 35.degree. C. for 6 hours. The volatiles were 
removed at reduced pressure at room temperature. A light yellow, viscous 
oil remained. A yield of 840 mg, approximately 100%, was obtained. Anal. 
Calcd. for (C.sub.9 H.sub.16 Si).sub.n : C, 70.97; H, 10.59. Found: C, 
71.49; H, 10.98. .sup.1 H NMR (C.sub.6 D.sub.6): .delta. 0.65-1.20 (m, 2H, 
SiCH.sub.2), 1.40-2.00 (m, approx. 3.5H, SiCH.sub.2 CH.sub.2 CH.sub.2 Si, 
SiCH.sub.2 CH.dbd.CH.sub.2), 4.90-5.28 (m, 2H, CH.sub.2 CH.dbd.CH.sub.2), 
5.65-6.28 (m, 1H, CH.sub.2 CH.dbd.CH.sub.2). .sup.13 C NMR {.sup.1 H}, 
(CDCl.sub.3): .delta..sub.c 16.0-19.0 (SiCH.sub.2 CH.sub.2 CH.sub.2 Si), 
19.0-21.0 (SiCH.sub.2 CH.dbd.CH.sub.2), 112.5-114.0 (SiCH.sub.2 
CH.dbd.CH.sub.2), 134.0-136.5 (SiCH.sub.2 CH.dbd.CH.sub.2). .sup.29 Si NMR 
{.sup.1 H}, (CDCl.sub.3): .delta..sub.Si -2.0-1.0 (SiCH.sub.2), -9.0 to 
-10.5 (SiH (weak)). Molecular Weight (VPO in benzene): M=2460 g/mol. 
Example 35 
The following example describes stepwise growth of a cascade dendrimer from 
(CH.sub.2 .dbd.CHCH.sub.2).sub.3 SiH in Et.sub.2 O including steps 35A, 
35B, and 35C. 
Step 35A 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 1.0 
mL of ether and 1 drop of the Karstedt catalyst. Then, over a 5 minute 
period, was added 0.84 g (5.52 mmol) of (CH.sub.2 .dbd.CHCH.sub.2).sub.3 
SiH by syringe. This mixture was stirred at 45.degree. C. for 6 hours. The 
ether was removed at reduced pressure at room temperature. A light yellow, 
viscous oil ("Product 35A") remained. A yield of 839 mg, approximately 
100%, was obtained. .sup.1 H NMR (C.sub.6 D.sub.6): .delta. 0.55-1.20 (m, 
2H, SiCH.sub.2), 1.30-2.00 (m, approx. 3.5H, SiCH.sub.2 CH.sub.2 CH.sub.2 
Si, SiCH.sub.2 CH.dbd.CH.sub.2), 4.85-5.25 (m, 2H, CH.sub.2 
CH.dbd.CH.sub.2), 5.60-6.25 (m, 1H, CH.sub.2 CH.dbd.CH.sub.2). .sup.13 C 
NMR {.sup.1 H}, (C.sub.6 D.sub.6): .delta. .sub.C 16.5-19.5 (SiCH.sub.2 
CH.sub.2 CH.sub.2 Si), 19.5-21.5 (SiCH.sub.2 CH.dbd.CH.sub.2), 113.0-114.5 
(SiCH.sub.2 CH.dbd.CH.sub.2), 134.5-136.0 (SiCH.sub.2 CH.dbd.CH.sub.2). 
.sup.29 Si NMR {.sup.1 H}, (C.sub.6 D.sub.6): .delta..sub.Si -2.5-1.0 
(SiCH.sub.2), -9.0 to -10.5 (SiH (weak)). Molecular Weight (VPO in 
toluene): M=2555 g/mol. 
Step 35B 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 504 
mg of Product 8A dendrimer prepared in the foregoing Step 8A and 0.2 mL of 
ether. This mixture was stirred in a bath at 45.degree. C. One drop of the 
Karstedt catalyst was added and, then, over a 1 hour period, was added 
0.84 g (5.52 mmol) of (CH.sub.2 .dbd.CHCH.sub.2).sub.3 SiH by syringe. 
This mixture was kept at 45.degree. C. for another 6 hours. The volatiles 
were removed at reduced pressure at room temperature. A light yellow oil, 
("Product 35B"), more viscous than Product 35A, remained. A yield of 1.34 
g, approximately 100%, was obtained. Anal. Calcd. for (C.sub.9 H.sub.16 
Si).sub.n : C, 70.97; H, 10.59. Found: C, 71.75; H, 10.86. .sup.1 H NMR 
(C.sub.6 D.sub.6): .delta. 0.55-1.20 (m, 2.3H, SiCH.sub.2), 1.30-2.05 (m, 
approx. 3.7H, SiCH.sub.2 CH.sub.2 CH.sub.2 Si, SiCH.sub.2 
CH.dbd.CH.sub.2), 4.85-5.30 (m, 2H, CH.sub.2 CH.dbd.CH.sub.2), 5.60-6.30 
(m, 1H, CH.sub.2 CH.dbd.CH.sub.2). .sup.13 C NMR {.sup.1 H}, (C.sub.6 
D.sub.6): .delta..sub.c 16.5-19.5 (SiCH.sub.2 CH.sub.2 CH.sub.2 Si), 
19.5-21.5 (SiCH.sub.2 CH.dbd.CH.sub.2), 113.0-114.5 (SiCH.sub.2 
CH.dbd.CH.sub.2), 134.5-136.0 (SiCH.sub.2 CH.dbd.CH.sub.2). .sup.29 Si NMR 
{.sup.1 H}, (C.sub.6 D.sub.6): .delta..sub.Si -2.5-1.0 (SiCH.sub.2), -7.5 
to -10.5 (SiH (weak)). Molecular Weight (VPO in toluene): M=5445 g/mol. 
Step 35C 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 513 
mg of Product 35B dendrimer prepared in the foregoing Step 35B and 0.5 mL 
of ether. This mixture was stirred in a bath at 45.degree. C. One drop of 
the Karstedt catalyst was added and, then, over a 1 hour period, was added 
0.42 g (2.76 mmol) of (CH.sub.2 .dbd.CHCH.sub.2).sub.3 SiH by syringe. 
This mixture was kept at 45.degree. C. for another 6 hours. The volatiles 
were removed at reduced pressure at 50.degree. C. A light brown, soluble 
gel ("Product 35C") remained. A yield of 0.93 g, approximately 100%, was 
obtained. .sup.1 H NMR (C.sub.6 D.sub.6): .delta. 0.50-1.25 (m, approx. 
2.0H, SiCH.sub.2), 1.30-2.05 (m, approx. 3.5H, SiCH.sub.2 CH.sub.2 
CH.sub.2 Si, SiCH.sub.2 CH.dbd.CH.sub.2), 4.85-5.30 (m, 2H, CH.sub.2 
CH.dbd.CH.sub.2), 5.60-6.40 (m, 1H, CH.sub.2 CH.dbd.CH.sub.2). Molecular 
Weight could not be obtained because the product was not sufficiently 
soluble. 
Example 36 
The following example describes quenching of the cascade dendrimer from 
(CH.sub.2 .dbd.CHCH.sub.2).sub.2 MeSiH with Me.sub.3 SiCH.dbd.CH.sub.2. 
The two experiments described below were carried out to demonstrate 
deactivation of remaining Si--H bonds in the dendrimer. 
Synthesis 36A--30 Minute Dendrimer Synthesis 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 
1.22 g (9.66 mmol) of (CH.sub.2 .dbd.CHCH.sub.2).sub.2 MeSiH, 1.0 mL of 
ether, and 1 drop of the Karstedt catalyst. This mixture was stirred at 
35.degree. C. for 30 minutes. Then, 0.2 mL of Me.sub.3 SiCH.dbd.CH.sub.2 
was added by syringe. The reaction mixture was stirred for another 2.5 
hours. The volatiles were removed at reduced pressure at 50.degree. C. A 
light yellow, viscous oil, ("Product 36A"), remained. A yield of 1.25 g, 
approximately 98%, was obtained. .sup.1 H NMR (C.sub.6 D.sub.6): .delta. 
-0.05-0.30 (m, 3.5H, SiCH.sub.3, Si(CH.sub.3).sub.3), 0.35-1.00 (m, 
approx. 4.1H, SiCH.sub.2 SiCH.sub.2 CH.sub.2 Si, SiCH.sub.2 CH.sub.2 Si), 
1.35-1.90 (m, approx. 4.1H, SiCH.sub.2 CH.dbd.CH.sub.2, SiCH.sub.2 
CH.sub.2 CH.sub.2 Si) 4.85-5.14 (m, 2H, CH.sub.2 CH.dbd.CH.sub.2), 
5.70-6.20 (m, 1H, CH.sub.2 CH.dbd.CH.sub.2). 
Synthesis 36B--2 Hour Dendrimer Synthesis 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 
1.20 g (9.66 mmol) of (CH.sub.2 .dbd.CHCH.sub.2).sub.2 MeSiH, 1.0 mL of 
ether, and 1 drop of the Karstedt catalyst. This mixture was stirred at 
35.degree. C. for 2 hours. Then, 0.2 mL of Me.sub.3 SiCH.dbd.CH.sub.2 was 
added by syringe. The reaction mixture was stirred for another hour. The 
volatiles were removed at reduced pressure at 50.degree. C. A light yellow 
oil, more viscous than Product 36A, remained. A yield of 1.22 g, 
approximately 98%, was obtained. .sup.1 H NMR (C.sub.6 D.sub.6): .delta. 
0.05-0.35 (m, 3.3H, SiCH.sub.3, Si(CH.sub.3).sub.3, 0.45-1.10 (m, approx. 
4.2H, SiCH.sub.2 SiCH.sub.2 CH.sub.2 Si, SiCH.sub.2 CH.sub.2 Si), 
1.35-1.88 (m, approx. 4.25H, SiCH.sub.2 CH.dbd.CH.sub.2, SiCH.sub.2 
CH.sub.2 CH.sub.2 Si), 4.85-5.13 (m, 2H, CH.sub.2 CH.dbd.CH.sub.2), 
5.65-6.20 (m, 1H, CH.sub.2 CH.dbd.CH.sub.2). 
Example 37 
The following example describes chemical conversions of a cascade dendrimer 
prepared from (CH.sub.2 .dbd.CH).sub.2 MeSiH. 
Conversion 37A 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 740 
mg of a dendrimer prepared from (CH.sub.2 .dbd.CH).sub.2 MeSiH as 
described in the foregoing Example 3 and 0.5 mL of ether. This mixture was 
stirred in a bath at room temperature. Then, 0.5 mL (434 mg, 4.59 mmol) of 
HSiMe.sub.2 Cl was added. The reaction started spontaneously and the 
temperature increased. The mixture was stirred at 35.degree. C. for 2 
hours. The volatiles were removed at reduced pressure at 50.degree. C. A 
colorless, viscous oil ("Product 37A") remained. A yield of 1.0 g, 
approximately 100%, was obtained. .sup.1 H NMR (CDCl.sub.3): .delta. 
0.20-0.02 (s(overlapped), 2.7H, SiCH.sub.3), 0.38 (s, 6H, SiCH.sub.3 Cl), 
0.44-1.14 (m, 5.6H, SiCH.sub.2). 
Conversion 37B-Reduction of Product 10A 
Into a 20 mL flask equipped with a stir bar and rubber septum was added 1.0 
g of a chlorosilyl group containing Product 37A dendrimer prepared in the 
foregoing Conversion 37A and 2 mL of ether. This mixture was stirred in a 
bath at room temperature. Then, 100 mg (2.63 mmol) of LiAlH.sub.4, in 3 mL 
of ether was added slowly by syringe. An exothermic reaction occurred. The 
mixture was stirred at 35.degree. C. for 2 hours. Then, the reaction 
mixture was hydrolyzed with 5 mL of 0.5 M HCl. The solution was filtered 
through Celite.TM. (Celite 545.TM.), a diatomaceous earth purchased from 
Fisher Scientific Co., and washed twice with 3 mL of ether. The organic 
layer was washed with water and separated. After the solution was dried 
over MgSO.sub.4, all volatiles were removed at reduced pressure at 
50.degree. C. A colorless, viscous oil remained. A yield of 850 mg, 
approximately 94.4%, was obtained. Anal. Calcd. for (C.sub.7 H.sub.18 
Si.sub.2).sub.n : C, 53.08; H, 11.45. Found: C, 53.60; H, 11.36. .sup.1 H 
NMR (CDCl.sub.3): .delta. 0.00-0.35 (s(overlapped), 9.7H, SiCH.sub.3), 
0.48-1.35 (m, 8.7H, SiCH.sub.2), 4.10-4.27 (m, 1H, SiH). Molecular Weight 
(VPO in benzene): M=905 g/mol. 
Synthesis 37C--Preparation of a Dichlorozirconocene complex 
[--MeSi(CH.sub.2 CH.sub.2 --)(CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 
CH.sub.2 SiMe.sub.2 C.sub.5 H.sub.4 ](C.sub.5 H.sub.5)ZrCl.sub.2).sub.n 
approximately 6) 
Into a 20 mL flask equipped with a stir bar and rubber septum was added 244 
mg (0.65 mmol) of [(CH.sub.2 .dbd.CH)Me.sub.2 SiC.sub.5 H.sub.4 ] (C.sub.5 
H.sub.5)ZrCl.sub.2, 102 mg (approximately 0.65 mmol) of a Si--H 
group-containing dendrimer prepared in Conversion 10B, 0.5 mL of THF and 1 
drop of the Karstedt catalyst solution. This mixture was stirred at 
50.degree. C. for 6 hours. Then, all volatiles were removed at reduced 
pressure, and the residue was washed twice with 1 mL of hexane. The light 
brown, waxy product was dried in vacuum at 40.degree. C. A yield of 330 
mg, 95.4%, was obtained. Anal. Calcd. for (C.sub.21 H.sub.36 Cl.sub.2 
Si.sub.3 Zr).sub.n : C, 47.15; H, 6.78. Found: C, 48.26; H, 6.78. .sup.1 H 
NMR (CDCl.sub.3): .delta. -0.15-0.15 (s(overlapped), 11H, SiCH.sub.3), 
0.31 (s, 6H, CpSiCH.sub.3), 0.32-1.10 (m, approx. 12H, SiCH.sub.2), 6.46 
(s, 5H, C.sub.5 H.sub.5), 6.57 (m, 2H, C.sub.5 H.sub.4), 6.73 (m, 2H, 
C.sub.5 H.sub.4). .sup.13 C NMR {.sup.1 H}, (CD.sub.2 Cl.sub.2): 
.delta..sub.c -7.0-0.0 (SiCH.sub.3), 4.0-10.0 (SiCH.sub.2), 116.3 (C.sub.5 
H.sub.5), 117.7 (C.sub.5 H.sub.4), 125.7 (C.sub.5 H.sub.5), 126.0 (C.sub.5 
H.sub.5). .sup.29 Si NMR {.sup.1 H), (CD.sub.2 Cl.sub.2): .delta..sub.Si 
-3.99 (SiCp), 5.11 (Si(CH.sub.3).sub.2), 6.0-8.0 (SiCH.sub.3, CH.sub.2 
Si). 
Example 38 
The following example is provided to demonstrate the polymerization of 
ethylene using the zirconocene complex prepared in Synthesis 37C of the 
foregoing Example 37. 
A 250 mL three-necked flask equipped with reflux condenser, magnetic stir 
bar, inside thermometer and a gas inlet tube was filled with 100 mL of 
toluene, 0.66 mL MAO solution (10% intoluene) and 0.5 mL of a 
2.times.10.sup.-3 M solution of [--MeSi(CH.sub.2 CH.sub.2 --) (CH.sub.2 
CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 C.sub.5 H.sub.4 ](C.sub.5 
H.sub.5)ZrCl.sub.2).sub.n (n approximately 6) as described in Synthesis 
10C in toluene. This solution was stirred for 20 minutes to activate the 
catalyst. The catalyst solution was then heated to 45.degree. C. and held 
at this temperature. Ethylene was bubbled through the system for 15 
minutes. The reaction was stopped by addition of 50 mL of a methanol 
solution containing 0.5 mL of 1 M HCl. The polymer was then filtered and 
washed several times with 120 mL of methanol. Finally, the polymer was 
dried in vacuum at 40.degree. C. for 20 hours. A yield of 1.43 g 
polyethylene which corresponds to a catalyst activity of 5736 
kg/mol.times.hour (956 kg/mol(Zr).times.hour) was obtained. 
Example 39 
The following example describes preparation of a dendrimer starting with a 
Si(CH.dbd.CH.sub.2).sub.4 core and subsequent chemical conversions of the 
dendrimer. 
Synthesis 39A--Preparation of the Dendrimer 
Into a 10 mL flask equipped with a stir bar and rubber septum was added 209 
mg (1.53 mmol) of Si(CH.dbd.CH.sub.2).sub.4, 2 mL of THF and approximately 
1/10 of 775 mg (6.14 mmol) of (CH.sub.2 CH.dbd.CH.sub.2).sub.2 MeSiH. This 
mixture was stirred at room temperature. Then, 1 drop of the Karstedt 
catalyst was added. Over a period of 1 hour, the remainder of the 
(CH.sub.2 CH.dbd.CH.sub.2).sub.2 MeSiH was added slowly by syringe at room 
temperature. Then, the mixture was stirred at 50.degree. C. for 4 hours. 
All volatiles were removed at reduced pressure at 50.degree. C. A light 
yellow oil ("Product 39A") remained. A yield of 0.98 g, approximately 
100%, was obtained. Anal. Calcd. for (C.sub.36 H.sub.68 Si.sub.5).sub.n : 
C, 67.42; H 10.68. Found: C, 67.29; H, 10.74. .sup.1 H NMR (C.sub.6 
D.sub.6): .delta. 0.00-0.25 (s (overlapped), 3H, SiCH.sub.3), 0.50-0.85 
(m, 4H, SiCH,CH.sub.2 Si), 1.02-1.20 (m, approx. 1H, 20 CH.sub.2 CH.sub.2 
CH.sub.2 (byproduct of addition to allyl)), 1.58 (m, 4H, SiCH.sub.2 
CH.dbd.CH.sub.2), 4.83-5.04 (m, 4.8H, CH.sub.2 CH.dbd.CH.sub.2), 5.70-5.95 
(m, approx. 1H, CH.sub.2 CH.dbd.CH.sub.2), 5.95-6.25 (m, approx. 1H, 
SiCH.dbd.CH.sub.2). Molecular Weight (VPO in toluene): M=546 g/mol. 
Conversion 39B--Addition of Me.sub.2 SiHCl to Product 39A Dendrimer 
Into a 25 mL flask equipped with a stir bar and rubber septum was added 807 
mg (1.26 mmol) of "Si[CH.sub.2 CH.sub.2 SiMe(CH.sub.2 
CH.dbd.CH.sub.2).sub.2 ].sub.4 " as already described in Synthesis 39A and 
0.5 mL of ether. Then, 2.0 mL, (18.3 mmol) of Me.sub.2 SiHCl was added 
slowly. The reaction started spontaneously and the temperature increased. 
The mixture was stirred at 35.degree. C. for 6 hours. The volatiles were 
removed at reduced pressure at 50.degree. C. A colorless, viscous oil 
("Product 12B") remained. A yield of 1.75 g, approximately 100%, was 
obtained. .sup.1 H NMR (CDCl.sub.3): .delta. -0.10-0.15 (s(overlapped), 
3H. SiCH.sub.3), 0.38 (s, 12H, SiCH.sub.3 Cl), 0.50-0.72 (m, 4H, 
SiCH.sub.2 CH.sub.2 CH.sub.2 SiCl), 0.80-1.00 (m, 4H, SiCH.sub.2 CH.sub.2 
CH.sub.2 SiCl), 1.30-1.50 (m, 4H, SiCH.sub.2 CH.sub.2 CH.sub.2 SiCl). 
Conversion 39C--Reduction of Product 39B With LiAlH.sub.4 
Into a 25 mL flask equipped with a stir bar and rubber septum was added 
1.70 g (1.22 mmol) of Si[CH.sub.2 CH.sub.2 SiMe(CH.sub.2 CH.sub.2 CH.sub.2 
SiMe.sub.2 Cl).sub.2 ].sub.4 " as already described in Conversion 39B and 
3 mL of ether. Then, 300 mg (7.90 mmol) of LiAlH.sub.4 in 10 mL of ether 
was added slowly by syringe. A reaction started as the temperature was 
increased. The mixture was stirred at 35.degree. C. for 4 hours. Then, the 
reaction mixture was hydrolyzed with 10 mL of 0.5 M HCl. The solution was 
filtered through Celite.TM. (Celite 545.TM.), a diatomaceous earth 
purchased from Fisher Scientific Co., and washed twice with 3 mL of ether. 
The organic layer was washed with water and separated. After the solution 
was dried over MgSO.sub.4, all volatiles were removed at reduced pressure 
at 50.degree. C. A colorless, viscous oil ("Product 39C") remained. A 
yield of 1.15 g, 82%, was obtained. Anal. 4 Calcd. for C.sub.52 H.sub.132 
Si.sub.13 :C, 55.63; H, 11.85. Found: C, 55.87; H, 11.88. .sup.1 H NMR 
(C.sub.6 D.sub.6): .delta. 0.00-0.38 (s (overlapped), 15H, SiCH.sub.3), 
0.55-1.00 (m, 10H, SiCH.sub.2), 1.15-1.40 (m, approx. 2H, CH.sub.2 
(byproduct)), 1.50-1.90 (SiCH.sub.2 CH.sub.2 CH.sub.2 Si), 4.12-4.30 (m, 
1H, SiH). Molecular Weight (VPO in toluene): M=1024 g/mol. 
Synthesis 39D--Preparation of a Dichlorozirconocene complex 
[--MeSi(CH.sub.2 H.sub.2 --) (CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 
CH.sub.2 SiMe.sub.2 C.sub.5 H.sub.4 ] C.sub.5 H.sub.5)ZrCl.sub.2).sub.n (n 
approximately 6) 
Into a 20 mL flask equipped with a stir bar and rubber septum were added 
470 mg (1.25 mmol) of (CH.sub.2 .dbd.CH) Me.sub.2 Si(C.sub.5 
H.sub.4)C.sub.5 H,ZrCl.sub.2, 175 mg (0.16 mmol) of "Si[CH.sub.2 CH.sub.2 
SiMe(CH.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 H).sub.2 ].sub.4 " described 
already in Conversion 39C, 0.5 mL of THF and 2 drops of the Karstedt 
catalyst solution. This mixture was stirred at 50.degree. C. for 6 hours. 
Then, all volatiles were removed at reduced pressure, and the residue was 
washed twice with 1 mL of hexane. The light brown, waxy product ("Product 
39D") was dried in vacuum at 40.degree. C. A yield of 640 mg, 99%, was 
obtained. Anal. Calcd. for C.sub.164 H.sub.276,Cl.sub.8,Si.sub.21,Zr.sub.8 
: C, 51.15; H, 7.22. Found: C, 49.32; H, 7.03. .sup.1 H NMR (CDCl.sub.3) 
.delta. -0.09 (s, 12H, Si.sup.3 CH.sub.3), 0.01 (s, 3H, Si.sup.2 
CH.sub.3), 0.27 (s(overlapped), 12H, Si.sup.4 CH.sub.3), 0.25-0.70 (m, 
20H, Si CH.sub.2), 1.25 (m, 4H, CH.sub.2 CH.sub.2 CH.sub.2), 6.44 (s, 10H, 
C.sub.5 H.sub.5), 6.53 (m, 4H, C.sub.5 H.sub.4), 6.68 (m, 4H, C.sub.5 
H.sub.4). C NMR {.sup.1 H}, (CDCl.sub.3): .delta. -5.70 (Si.sup.2 
CH.sub.3), -3.89 (Si.sup.3 CH.sub.3), 2.96 (Si.sub.4 CH.sub.3), 3.5-10.5 
(SiCH.sub.2), 18.3 (SiCH.sub.2 CH.sub.2 CH.sub.2 Si), 115.71 (C.sub.5 
H.sub.5), 117.01 (C.sub.5 H.sub.4), 125.08 (C.sub.5 H.sub.4), 125.60 
(C.sub.5 H.sub.4). 
For the NMR analysis, Si atoms are numbered from the core outward toward 
the periphery of the dendrimer and that number indicated by a superscript 
to thecright of the Si chemical symbol. 
In the foregoing Example 39, the various "Si[ ].sub.4 " species are written 
within quotation marks because their molecular structure is not this 
regular. By NMR indications, some (CH.sub.2 CH.dbd.CH.sub.2).sub.2 MeSiH 
addition occurred to allyl instead of to vinyl groups. 
Example 40 
The following example is provided to demonstrate the polymerization of 
ethylene using the zirconocene complex prepared in Synthesis 39D of the 
foregoing Example 39. 
A 250 mL three-necked flask equipped with reflux condenser, magnetic stir 
bar, inside thermometer and a gas inlet tube was charged with 100 mL of 
toluene, 0.66 mL MAO solution (10% in toluene) and 0.5 mL of a 0.002 M 
solution of "Si[CH.sub.2 CH.sub.2 CH.sub.2 SiMe.sub.2 CH.sub.2 CH.sub.2 
SiMe.sub.2 (C.sub.5 H.sub.4)C.sub.5 H.sub.5 ZrCl.sub.2).sub.2 ].sub.4 " 
above Example 39 in toluene. This solution was stirred for 20 minutes to 
activate the catalyst. The catalyst solution was then heated to 45.degree. 
C. and held at this temperature. Ethylene was bubbled through the system 
for 15 minutes. The temperature increased to 60.degree. C. spontaneously 
during the reaction. The reaction was stopped by addition of 50 mL of a 
methanol solution containing 0.5 mL of 1 M HCl. The polymer was then 
filtered and washed several times with 200 mL of methanol. Finally, the 
polymer was dried in vacuum at 40.degree. C. for 20 hours. A yield of 3.10 
g polyethylene which corresponds to a catalyst activity of 12400 kg/mol 
hour (1550 kg/mol(Zr).times.hour) was obtained. 
In the foregoing Example 40, the various "Si[ ].sub.4 " species are written 
within quotation marks because their molecular structure is not this 
regular. By NMR indications, some (CH.sub.2 CH.dbd.CH.sub.2).sub.2 MeSiH 
addition occurred to allyl instead of to vinyl groups. 
Example 41 
The following example describes growth of a larger dendrimer than those 
described in the foregoing examples starting here from a tetrafunctional 
core. 
Into a 25 mL flask equipped with a stir bar and rubber septum was added 1.0 
g (1.56 mmol) of Si[CH.sub.2 CH.sub.2 SiMe(CH.sub.2 CH.dbd.CH.sub.2).sub.2 
].sub.4, prepared as described in Example 39, 1.0 mL of ether and 1 drop 
of the Karstedt catalyst. Over a period of 8 hours, 1.575 g (12.47 mmol) 
of (CH.sub.2 CH.dbd.CH.sub.2).sub.2 MeSiH was added slowly by syringe at 
40.degree. C. Then, the mixture was stirred at 45.degree. C. for 24 hours. 
The ether was removed at reduced pressure at 45.degree. C. A light yellow, 
viscous oil remained. A yield of 2.57 g, approximately 100%, was obtained. 
.sup.1 H NMR (C.sub.6 D.sub.6): .delta. -0.05-0.40 (m, 36H, SiCH3), 
0.50-1.30 (m, 48H, SiCH.sub.2 CH.sub.2 CH.sub.2 Si, SiCH.sub.2 CH.sub.2 
Si), 1.35-1.90 (m, 48 H, SiCH.sub.2 CH.sub.2 CH.sub.2 Si,SiCH.sub.2 
CH.dbd.CH.sub.2), 4.95-5.15 (m, 32H, CH.sub.2 CH.dbd.CH.sub.2), 5.65-6.20 
(m, 16H, CH.sub.2 CH.dbd.CH.sub.2). Molecular Weight (by GPC): M.sub.n 
=1611 g/mol, M.sub.W =2113 g/mol, M.sub.w /M.sub.n =1.31 where M.sub.n, 
represents the number average molecular weight and M.sub.W represents the 
weight average molecular weight.