Insoluble metallic complexes and catalysts therefrom

Solid catalyst, insoluble in organic and aqueous solvents and having the general formula: EQU A -- M (L').sub.n (L").sub.q in which A is an insoluble ligand, M is a Group VIII noble metal, L' and L" are ligands and n and q are intergers of 0 to 6 are provided for the advantageous catalysis of hydroformylation, and hydrogenation of olefins and the preparation of tertiary amines from olefins.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to new insoluble metallic complexes and to 
their use as catalysts in various reactions such as hydroformylation, 
hydrogenation and the preparation of tertiary amines by the reaction of an 
olefin, carbon monoxide and hydrogen with a secondary amine. 
2. Description of the Prior Art 
Generally, the catalysts employed in such reactions are soluble catalysts 
derived from Group VIII noble metals which are difficult to recover 
because the active catalyst is present in the form of coordination 
complexes which are dissolved in the reaction medium. 
Insoluble catalysts forming heterogeneous catalyst-reaction medium systems 
and obtained from soluble complexes of noble metals have heretofore been 
used in various reactions. For example, insoluble ligands prepared from 
organic polymers with particular functional groups thereon, such as 
amines, phosphines (French Pat. No. 1,583,037, filed Oct. 1, 1968) and 
vinylpyridine (U.S. Pat. No. 3,636,159, filed Dec. 19, 1968) have been 
proposed. Likewise, inorganic compounds into which a phosphor-containing 
radical has been introduced, either on silica or alumina (British Pat. No. 
1,275,733) or an alkoxysilane having a phosphine group thereon or a 
metallic complex of this alkoxysilane with silica (French patent 
application Ser. No. 70/45 824, now French Pat. No. 2,071,942, filed Dec. 
18, 1970), have been suggested for the hydroformylation of ethylenically 
unsaturated hydrocarbons to yield aldehydes and alcohols (French patent 
application Ser. No. 70/45 607, now French Pat. No. 2,073,940, filed Dec. 
17, 1970). 
The advantage of such catalysts is that the precious, relatively expensive 
metals therein remain complexed and are not released into the effluent of 
the reactor and are easily recovered therefrom in their original 
catalytically active form. 
The capacity of these solid catalysts to retain the metal after reaction is 
due to the coordinating element of the insoluble ligand and not to other 
coordinating elements ultimately associated with the metal but not 
directly linked to the insoluble ligand. 
Up to the present time, in such catalysts, phosphorus was generally used as 
a donor heteroatom, and was linked to an inorganic or organic, polymeric 
matrix. Although these catalysts display satisfactory catalytic activity, 
the metal retention properties of same have rendered such catalysts 
economically unsuitable for commercial applications. 
SUMMARY OF THE INVENTION 
The present invention relates to solid catalysts, insoluble in organic 
solvents and water, which are of the metallic complex type and comprise an 
insoluble ligand, a noble metal of Group VIII and other ligands linked to 
this noble metal and having the following general formula: 
EQU A -- M (L').sub.n (L").sub.q 
wherein A is an insoluble ligand prepared by reacting an alkoxysilane or a 
chlorosilane which contains an amine radical or a carboxylic acid radical 
with silica or alumina or by reacting a vinylalkoxysilane or a 
vinylchlorosilane and then copolymerizing the resultant product with 
vinylpyridine; M is a noble metal of Group VIII; L' and L" are identical 
or different ligands such as chlorine, carbon monoxide, olefins, and 
hydrocarbyl substituted amines, phosphines, phophites and arsines; and n 
and q are integers between about 0 and 6. 
It is, therefore, a primary object of the present invention to provide 
insoluble metallic complexes which display a high degree of catalytic 
activity of olefin conversion reactions. 
A further object of the instant invention is to provide catalytically 
active metallic complexes wherein the metal thereof remains complexed with 
the coordinating element of an insoluble ligand and is not released into 
the effluent from the reactor. 
Still another object of the invention is the preparation of a catalytic 
insoluble metallic complex suitable for the catalysis of olefin conversion 
to aldehydes, alcohols and tertiary amines which complex may be recycled 
and reused in subsequent reactions without any noticeable reduction in the 
catalytic activity of the recycled complex. 
Other objects, features and advantages of this invention will become more 
apparent to those skilled in the art from the detailed description of the 
preferred embodiments which follows. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The catalysts of the present invention have a high metal retention capacity 
which significantly enhances the economic feasability of utilizing same on 
a commercial scale. 
The catalysts of the present invention may be prepared and isolated by 
either of the two following methods: First, by the reaction of a salt or a 
coordination complex of a noble metal of Group VIII with an insoluble 
ligand such as described hereinabove. The noble metals of Group VIII are 
ruthenium, rhodium, palladium, osmium, iridium and platinum. The insoluble 
ligands may be obtained, for example, by reacting silica or alumina with 
an alkoxysilane or chlorosilane having from 1 to 20 carbon atoms and 
having a radical comprising an amine or carboxylic acid function. 
The radical comprising an amine function is derived from a primary, 
secondary or tertiary mono-amine or polyamine. Their substituents have 
from 1 to 20 carbon atoms and are selected from the group consisting of 
alkyl, cycloalkyl, aryl, aryloxy, aralkyl and alkaryl radicals. Suitable 
radicals are: (amino 2 ethyl)amino, aminophenoxy, methylaminophenoxy, 
dimethylaminophenoxy, aminophenyl, methylaminophenyl, dimethylaminophenyl, 
phenylaminophenyl, diphenylaminophenyl, methylphenylaminophenyl, 
methylamino-, ethylamino-, dimethylamino-, diethylamino-, anilino-, 
diphenylamino-, methylphenylamino-, (dimethylamino 2)ethyl, 
cyclohexylamino-, methylaminocyclohexyl-, dimethylaminocyclohexyl, 
aminocyclohexyl, piperidyl, methylpiperidyl, pyridil, pyridyl 2 ethyl, 
pycolyl. 
The radical comprising a carboxylic acid function hat from 1 to 20 carbon 
atoms and is selected from the group consisting of alkylcarboxylic, 
alkenylcarboxylic, arylcarboxylic, alkaryl carboxylic and aralkyl 
carboxylic radicals. Suitable radicals are: 
phenylcarboxylic: -- C.sub.6 H.sub.4 -- COOH 
acrylic: -- CH.dbd.CH -- COOH 
acetic: -- CH.sub.2 -- COOH 
propionic: -- CH.sub.2 -- CH.sub.2 -- COOH 
toluic: -- CH.sub.2 -- C.sub.6 H.sub.4 -- COOH 
new compounds such as those described in commonly owned French Patent 
Application No. 73/25 698, now French Patent No. 2,236,552 filed July 13, 
1973, corresponding to U.S. Pat. No. 3,969,261, are also useful. These 
compounds are anionic ion exchangers on mineral substrates and consisting 
of organic groups grafted by means of silicon atoms onto inorganic porous 
substrates having hydroxyl groups at their surfaces. The organic groups 
comprise one or more silicon atoms and aminated functions separated from 
silicon atoms by organic groups including at least three carbon atoms. 
Compounds described in commonly owned French patent application No. 73/29 
950, now French Pat. No. 2,245,663 filed Aug. 17, 1973, corresponding to 
U.S. Pat. No. 4,049,691, may also be used. These are aromatic, aminated 
silanes, the formula of which is as follows: 
##STR1## 
wherein p is an integer between about 2 and 4, X is a linear or branched 
chain alkoxy group having 1 to 8 carbon atoms; Y and Y' may be identical 
or different and represent a methyl, ethyl or phenyl group, or a linear or 
branched chain alkoxy group of about 1 to 8 carbon atoms. Dimers and 
linear or cross-linked polymers of such silanes may, likewise, be 
utilized. 
Ligands represented by L' and L" in the general formula are the same or 
different and can be chlorine, carbon monoxide, olefins and hydrocarbyl 
substituted amines, phosphines, phosphites and arsines represented by the 
formulas: 
EQU R'R"R'" N (R'O) (R"O) (R'" O) P 
EQU r'r"r'" p r'r"r'" as 
wherein R'R"R'" identical or different are H or hydrocarbyl moieties having 
from 1 to 20 carbon atoms selected from the group consisting of alkyl, 
cycloalkyl, aryl, aralkyl and alkaryl. 
Suitable ligands which may be used in accordance with this invention 
include: trimethylphosphine, triethylphosphine, tributylphosphine, 
triphenylphosphine, phenyldimethylphosphine, methyldiethylphosphine, bis 
diphenylphosphinoethane, tricyclohexylphosphine, trimethylphosphite, 
tributylphosphite, triphenylphosphite, trinonylphenylphosphite, 
tricyclohexylphosphite, phosphite de trimethylolpropane, trimethylamine, 
tributylamine, triphenylamine, phenyldethylamine, toluidine, aniline, 
methylamine, dimethylamine, ethylamine, cyclohexylamine, cyclohexylamine, 
phenylethylamine, triphenylarsine, triethylarsine, ethylene, cyclooctene, 
cyclooctadiene, norbornadiene. 
Alternatively, the insoluble ligand may be obtained by reacting a 
vinylalkoxysilane or a vinylchlorosilane with silica or alumina, and then 
copolymerizing the resultant product with vinylpyridine or acrylic acid, 
according to known methods. 
The second method of preparing the insoluble catalysts of the present 
invention is by the reaction of a salt or a coordination complex of a 
noble metal of Group VIII with a chlorosilane or an alkoxysilane having an 
amine or carboxylic acid function in order to obtain a different 
coordination complex which is then reacted, in a second step, with an 
inorganic solid compound containing hydroxyl groups, such as silica or 
alumina. The catalyst may be used after isolation or prepared "in situ". 
by introducing the insoluble ligand and the salt or metallic complex 
simultaneously into the reactor. 
When the salt or metallic complex used for the preparation of the catalyst 
does not comprise ligand containing trivalent phosphorus or arsenic such 
as phosphines, phosphites or arsines, the addition of such a ligand may be 
advantageous in order to increase the catalytic activity of the system, if 
necessary. The phosphorus or arsenic so added is not part of the insoluble 
ligand.

The following non-limitative examples are illustrative of the present 
invention. 
First, examples of the preparation of ligands such as those described 
hereinabove will be given followed by exemplary reactions of these ligands 
with a salt or a coordination complex of a noble metal of Group VIII. 
Preparation of Ligand A 
Into 500 ml xylene are introduced 500 g balls of silica gel (specific area 
415 m.sup.2 /g) previously dried under reduced pressure at 150.degree. C., 
for 4 hours and 100 g of the silane 
##STR2## 
The mixture is heated under stirring, at 190.degree. C. for 8 hours, and 
is filtered. After washing with acetone and drying under reduced pressure 
at 120.degree. C. for 4 hours, the solid product obtained contains 7% of 
carbon, 1% of nitrogen and the degree of exchange is 0.4 meq./g. 
Preparation of Ligand B 
The procedure used for ligand A is repeated, except 500 g balls of silica 
gel and 100 g of the silane 
##STR3## 
are introduced. The product obtained contains 0.8% of nitrogen. 
Preparation of Ligand C 
The procedure used for ligand A is repeated except 500 g balls of silica 
gel and 100 g of the silane 
EQU NH.sub.2 -- CH.sub.2 -- CH.sub.2 -- NH -- (CH.sub.2).sub.3 -- Si 
(OMe).sub.3 
are introduced. The product obtained contains 2% of nitrogen. 
Preparation of Ligands D, E, F 
These ligands were prepared according to the method of F. Runge et al., 
Macromolecular Chem., 1965, 81, p. 68. 
Ligand D 
Vinyltrichlorosilane is reacted with balls of silica gel (specific area 400 
m.sup.2 /g). The product obtained is copolymerized with 4-vinylpyridine. 
The resulting product contains 1.6% of nitrogen. 
Ligand E 
The procedure used for ligand D is repeated except alumina is used instead 
of silica. The product obtained contains 0.7% of nitrogen. 
Ligand F 
Vinyltrichlorosilane is reacted with balls of silica gel (specific area 400 
m.sup.2 /g). The product obtained is then copolymerized with acrylic acid. 
The examples hereinbelow further describe the preparation of catalysts 
according to the invention utilizing the above ligands as starting 
materials. 
All of the preparations are carried out under nitrogen free of oxygen, and 
the solvents were dried on molecular sieves and degased with nitrogen. 
EXAMPLE 1 
37.8 mg of Rh.sub.2 Cl.sub.2 (CO).sub.4 [dichlorotetracarbonyldirhodium] 
are introduced into a suspension of 2 g of ligand A in 20 ml of toluene. 
The mixture is stirred for a few minutes at room temperature, then for one 
hour at 50.degree. C. A brown solid is obtained by decantation, washed 
with toluene, hexane and dried under reduced pressure for 24 hours. The 
complex contains 1% by weight of rhodium. 
EXAMPLE 2 
180 mg of RhCl (PPh).sub.3 [tris (triphenylphosphine) chlororhodium] are 
introduced into a suspension of 2 g of ligand A in 20 ml of toluene. The 
mixture is stirred for 10 minutes at room temperature, then for 2 hours at 
80.degree. C. A liquid, slightly yellow-colored phase is obtained by 
decantation, and a solid product which is washed three times with 10 ml of 
toluene at 80.degree. C., then with 10 ml of hexane is also obtained. 
After drying under reduced pressure for 24 hours at room temperature, the 
resultant complex obtained contains 0.8% of rhodium. 
EXAMPLE 3 
52 mg of hydrated ruthenium trichloride containing 20 g of ruthenium are 
introduced into a suspension of 2 g of ligand A in 20 ml of ethanol. The 
mixture is stirred at room temperature for 10 minutes, then for 1 hour and 
30 minutes at 80.degree. C. A solid product and a liquid colorless phase 
are obtained by decantation. The solid product is washed three times with 
ethanol and dried under reduced pressure at room temperature for 24 hours. 
The solid compound obtained contains 1% by weight of ruthenium. 
EXAMPLE 4 
A catalyst containing 0.1% of Rh is prepared by the reaction of 4.1 mg of 
Rh.sub.2 Cl.sub.2 (CO).sub.4 with 2.2 g of ligand B. The isolation 
procedure of Example 1 is repeated. 
EXAMPLE 5 
A catalyst containing 0.93% of Rh is prepared by the reaction of 29.3 mg of 
RhCl(CO).sub.2 p-toluidine [paratoluidine dicarbonylchlororhodium] with 1 
g of ligand B. The recovery procedure of Example 2 is repeated. 
EXAMPLE 6 
A catalyst containing 1% of Rh is prepared by the reaction of 38 mg of 
Rh.sub.2 Cl.sub.2 (CO).sub.4 with 2 g of ligand C. The recovery procedure 
of Example 1 is repeated. 
EXAMPLE 7 
A solid catalyst containing 1% of Rh is prepared by reaction of 38 mg of 
Rh.sub.2 Cl.sub.2 (CO).sub.4 with 2 g of ligand D. The isolation procedure 
of Example 2 is followed. 
EXAMPLE 8 
A solid catalyst containing 1% of Rh is prepared by the reaction of 70 mg 
of Rh.sub.2 Cl.sub.2 (C.sub.8 H.sub.14).sub.4 
[tetracyclooctenedichlorodirhodium] with 2 g of ligand D. The recovery 
procedure of Example 2 is repeated. 
EXAMPLE 9 
70 mg of Rh.sub.2 Cl.sub.2 (C.sub.8 H.sub.14).sub.4 are introduced into a 
suspension of 2 g of ligand D. The mixture is heated at 80.degree. C., 
under stirring, for 15 minutes, then 54 mg of triphenylphosphine 
(PPh.sub.3) in 29 ml of toluene are added. The stirring is continued at 
80.degree. C. for 2 hours. A liquid colorless phase is obtained by 
decantation along with a solid product which is washed with toluene, then 
hexane. After drying under reduced pressure for 24 hours, at room 
temperature, a solid, yellow-colored product is obtained containing 0.93% 
of Rh. 
EXAMPLE 10 
A catalyst prepared as described in Example 8, 265 mg is introduced into 5 
ml of toluene to form a suspension. Then 8.1 mg of P(OPh).sub.3 in 10 ml 
of toluene are added to this suspension with stirring. The mixture is 
heated at 80.degree. C. for 1 hour and 30 minutes and the solid obtained 
by decantation is washed with warm toluene (2 .times. 10 ml) then with 
hexane and dried under vacuum. The catalyst so prepared contains 1% of 
rhodium. 
EXAMPLE 11 
A catalyst containing 0.125% of Rh is prepared by reacting 39.5 mg of 
Rh.sub.2 Cl.sub.2 (CO).sub.4 with 1.990 g of ligand E. The purification 
procedure of Example 2 is repeated. 
EXAMPLE 12 
A catalyst containing 0.4% of platinum is prepared by the reaction of 148 
mg of Pt [P(OPh).sub.3 ].sub.4 [tetrakis triphenylphosphite platinum] with 
2 g of ligand E. The recovery procedure of Example 2 is repeated. 
EXAMPLE 13 
A catalyst containing 0.1% of Rh is prepared by the reaction of 7.7 mg of 
Rh.sub.2 Cl.sub.2 (C.sub.8 H.sub.14).sub.4 with 2.2 g of ligand F. The 
isolation procedure of Example 2 is repeated. 
EXAMPLE 14 
A catalyst containing 0.3% of Rh is prepared by reacting 39.8 mg of 
Rh.sub.2 Cl.sub.2 (CO).sub.4 with 2 g of ligand F. The purification 
procedure of Example 2 is repeated. 
EXAMPLE 15 
A catalyst containing 0.63% of palladium is prepared by reacting 73 mg of 
PdCl.sub.2 (PhCN).sub.2 [bis-benzonitriledichloropalladium] with 2 g of 
ligand F. The recovery procedure of Example 2 is repeated. 
EXAMPLE 16 
28 mg of soluble ligand 
##STR4## 
are introduced into a solution of 18.9 mg of Rh.sub.2 Cl.sub.2 (CO).sub.4 
in 10 ml of xylene. The mixture is stirred for one hour at 50.degree. C. 
The obtained solution is then added to a suspension of 1 g of silica 
(specific area 400 m.sup.2 /g) in 10 ml of toluene. The stirring is 
continued for 4 hours at 80.degree. C. A solid product is obtained by 
decantation, and washed with toluene, then hexane. After drying under 
reduced pressure, the isolated product contains 1% of Rh. 
EXAMPLE 17 
A catalyst containing 1% of Rh is prepared by the reaction of 100 mg of 
RhCl.sub.3 (Py).sub.3 [tripyridinetrichlororhodium] with 2 g of ligand D. 
The recovery procedure of Example 3 is repeated. 
UTILITY 
The catalyst of the instant invention are particularly effective in the 
following reactions: 
-- hydroformylation of olefins to aldehydes and alcohols with a conversion 
rate between 30 and 99%. 
-- preparation of tertiary amines from olefins with considerable 
selectivity in favor of amines (70 to 98% relative to consumed olefin) 
-- hydrogenation of olefins to form higher alkanes with conversion rates 
from about 40% to 95% and of nitro-compounds to form corresponding higher 
amines with a conversion rate approaching 90%. 
The present catalysts are also active under moderated pressure conditions. 
Consequently, hydroformylation may be effectuated at under 10 to 120 bars 
(preferably from 20 to 90 bars) with solvents such as ketones, alcohols, 
ethers and hydrocarbons, particularly saturated hydrocarbons. Similarly, 
the preparation of tertiary amines may be carried out under 30 to 120 bars 
(preferably from 60 to 120 bars) with solvents such as alcohols, ethers 
and hydrocarbons, particularly saturated hydrocarbons. Likewise, the 
hydrogentation of olefins may be conducted from about 1 to 100 bars and 
preferably from 20 to 50 bars with the same solvents. 
The reaction temperature of the various catalytic reactions are generally 
below 220.degree. C. and preferably between about 100.degree. and 
200.degree. C. 
The use of coordinate complexes or ligands of noble metals results in a 
significant reduction in the concentration of metal present in the liquid 
effluent at the end of the reaction (on the order of ppm with respect to 
the product which is obtained in the case of hydroformylation or 
hydrogenation). This is one of the important improvements resulting from 
the utilization of the insoluble noble metal complexes of the invention. 
The following examples further illustrate the use of the catalysts 
according to the invention in the aforementioned reactions. 
EXAMPLES 18-30 
Hydroformylation Reactions 
10 ml of olefin, 10 ml of solvent and 200 mg of catalysts are introduced 
into a reactor equipped with gas injection, stirring and heating devices. 
Carbon monoxide and hydrogen are then injected at stated partial 
pressures. The mixture is then heated to the desired temperature and 
maintained for 5 hours with stirring. After cooling and pressure release 
the catalyst is separated by decantation. Then, the liquid phase is 
analyzed by vapor phase chromatography and the amount of olefin consumed, 
and the amounts of aldehydes and alcohols formed are determined. The 
concentration of metal in the reactive effluent is determined by flame 
emission spectrophotometry. 
The results are set forth in Table I hereinbelow. 
TABLE I 
__________________________________________________________________________ 
(Hydroformylation) 
Conversion rate 
of the olefin 
Metal concentration 
into into 
of the liquid phase 
Example 
Olefin 
Catalyst 
Solvent 
H.sub.2 (bars) 
CO (bars) 
T.degree. C 
aldehyde 
alcohol 
effluent in 
__________________________________________________________________________ 
ppm 
18 1-Octene 
Example 1 
Toluene 
45 45 150 
77 -- 3.5 
19 3-Pentene 
Example 2 
Heptane 
20 20 150 
64 -- 4.0 
20 1-Hexene 
Example 7 
Heptane 
45 45 150 
89 7 0.5 
21 1-Decene 
200 mg 
Toluene 
45 45 150 
87 (85) 
10 (5) 
4 (3) 
ligand 
D + 4 mg 
Rh.sub.2 Cl.sub.2 
(CO).sub.4 
22 1-Hexene 
Example 8 
Toluene 
20 20 150 
32 -- &lt; 0.5 
23 1-Hexene 
Example 9 
Toluene 
20 20 150 
56 (56) 
-- 0.8 (&lt;0.5) 
24 1-Hexene 
Example 10 
Toluene 
20 20 150 
66 -- 2.5 
25 1-Hexene 
Example 9 
Toluene 
20 20 150 
86 -- 2.7 
+5.7 mg 
(OPh).sub.3 
26 1-Hexene 
Example 1 
Toluene 
45 45 100 
51 -- 7.5 
27 1-Hexene 
Example 12 
Heptane 
45 45 150 
30 -- &lt; 2.0 
28 1-Hexene 
Example 13 
Toluene 
45 45 150 
52 (84) 
25 (-) 
29 1-Hexene 
Example 11 
Toluene 
45 45 150 
75 (87) 
14 (10) 
30 1-Hexene 
Example 16 
Toluene 
45 45 150 
79 
__________________________________________________________________________ 
The numbers in parentheses pertain to tests which were carried out with 
the catalyst recovered after the initial reaction. The reactor was brough 
to room temperature after completion of the reaction in Examples 19, 20 
and 27. For the other examples, the reactor was cooled to -80.degree. C. 
(at the end of the reaction). Example 28 contained 2,000 mg of catalyst. 
EXAMPLES 31-36 
Preparation of Tertiary Amines 
6.7 g of olefin, 10 ml of solvent, 3.6 g of dimethylamine and a given 
weight of catalyst are introduced into a reactor. The mixture is then 
heated at 150.degree. C. for 2 hours (or for 5 hours as described in 
Example 32). After completion of the reaction, the apparatus is cooled in 
a bath of acetonecarbonic acid before releasing the pressure. The amounts 
of amines formed are determined by vapor phase chromatography. 
The results are given in Table II hereinbelow. 
TABLE II 
__________________________________________________________________________ 
(Tertiary Amines) 
Catalyst 
Example 
Olefin 
Example 
Weight 
H.sub.2 (bars) 
CO (bars) 
Solvent 
.alpha. 
S [M] 
__________________________________________________________________________ 
31 1-Hexene 
1 200 mg 
60 60 Toluene 
100 
95 
15 
32 1-Decene 
3 200 mg 
90 30 Ethanol 
75 77 
-- 
33 1-Hexene 
4 2,000 mg 
60 60 Toluene 
98 97 
7 
34 1-Dodecene 
5 220 mg 
60 60 Toluene 
98 98 
20 
35 1-Hexene 
6 200 mg 
60 60 Toluene 
100 
96 
28 
36 1-Hexene 
14 670 mg 
60 60 Toluene 
97 75 
-- 
__________________________________________________________________________ 
.alpha. = Conversion rate of olefin 
S = Selectivity toward tertiary amines relative to consumed 
[M] = Metal concentration in the liquid phase effluent after reaction, 
expressed in ppm. The amount of catalyst used corresponds to 2 mg of meta 
 
EXAMPLES 37-42 
Hydrogenation Reactions 
Hydrogenation reactions can be carried out using various starting materials 
such as linear, branched or cyclic olefins and aliphatic or aromatic 
nitro-compounds. 
The starting material, solvent and catalyst are introduced into a reactor 
and hydrogen is injected under the desired pressure. The mixture is heated 
to the desired temperature for the desired reaction time. 
The results are given in Table III hereinbelow. 
TABLE III 
__________________________________________________________________________ 
(Hydrogenation) 
Duration 
Catalyst Unsaturated of Product Obtained 
[M] 
Example 
Example 
Weight 
Starting Material 
Solvent H.sub.2 (bars) 
Reaction 
(1) (2) 
__________________________________________________________________________ 
37 1 800 mg 
1-Hexene (40 ml) 
Toluene (40 ml) 
20 3 h 40' 
Hexane - 94% 
0.5 ppm Rh 
38 1 800 mg 
Nitrobenzene 
Toluene (40 ml) 
20 7 h Aniline - 96% 
0.5 ppm Rh 
(40 ml) 
39 3 200 mg 
1-Octene (10 ml) 
Heptane (10 ml) 
20 3 h Octane - 74% 
3 ppm Ru 
40 8 800 mg 
1-Hexene (40 ml) 
Toluene (40 ml) 
20 3 h Hexane - 94% 
0.5 ppm Rh 
41 12 500 mg 
1-Hexene (10 ml) 
Heptane (10 ml) 
20- 4 h Hexane - 38% 
&lt; 2 ppm Pt 
40+ 1 h 30 
42 15 312 mg 
1-Decene (10 ml) 
Heptane (10 ml) 
20 5 h Decane - 66% 
&lt; 1 ppm Pd 
__________________________________________________________________________ 
5 
All the tests were carried out at 100.degree. C. At the end of the 
reaction, the reactor is cooled to room temperature (Examples 39, 41, 42) 
or to -80.degree. C. (Examples 37, 38, 40). 
(1) Conversion rate of unsaturated compound to hydrogenated product 
(2) [M] = Metal concentration in the liquid phase after reaction 
The catalysts used in the various reactions described hereinabove are 
easily recovered and may be used repeatedly without loss of catalytic 
activity. For instance, a hydroformylation reaction was carried out with 
the catalyst of Example 8 with recovery of the catalyst and subsequently 
20 hydroformylation reactions were conducted with the same recycled 
catalyst. 
Thus, there is provided by the present invention catalytically active 
insoluble metallic complexes having an insoluble ligand moiety 
coordinately complexed with a Group VIII noble metal which are extremely 
valuable for the catalysis of hydroformylation and hydrogenation reactions 
and the preparation of tertiary amines from olefins and wherein the noble 
metal of the complex remains in complexed form to substantially prevent 
any loss of the metal in the reactor effluent or any reduction in the 
catalytic activity of the complex upon completion of the reaction whereby 
the metallic insoluble catalyst complex may be recovered and utilized in 
subsequent reactions. 
While the invention has been described and illustrated with reference to 
certain preferred embodiments thereof, those skilled in the art will 
appreciate that various changes, modifications and substitutions therein 
can be made without departing from the spirit of the invention. It is 
intended, therefore, that the invention be limited only by the scope of 
the claims which follow.