Patent GB-1265564-A (GB)
IPC: C07F15/00
Filed: 1969-07-17
Abstract: 1,265,564. Organometallic silicon compounds. NATIONAL RESEARCH DEVELOPMENT CORP. 15 July, 1970 [17 July, 1969], No. 36021/69. Heading C3S. [Also in Division C2] Novel organometallic compounds have the formula L n M[CY m (M<SP>1</SP>R<SP>1</SP>R<SP>2</SP>R<SP>3</SP>) 3-m ] r , wherein M represents a transition metal of Group IVa, Va, VIa, VIIa, VIII or Ib of the Periodic Table of the elements; M<SP>1</SP> represents carbon, silicon, germanium, tin or lead; m is 0, 1 or 2; Y represents hydrogen, halogen, alkyl or aryl; when M<SP>1</SP> is carbon R<SP>1</SP>, R<SP>2</SP> and R<SP>3</SP> represent alkyl or aryl groups; when M<SP>1</SP> is silicon, germanium, tin or lead R<SP>1</SP>, R<SP>2</SP> and R<SP>3</SP> represent hydrogen, halogen or alkyl, aryl, alkoxy or aralkoxy groups; r is 1 or more depending on the available valencies of the transition metal; and Ln is the sum of all other ligands (if any) to the transition metal. Such other ligands may be CO, trialkyl or triaryl phosphines, olefins, cyclopentadiene, acetylene, halogens or alkoxy groups. The above compounds are prepared (1) by reacting a compound L n MX, with a compound (R<SP>1</SP>R<SP>2</SP>R<SP>3</SP>M<SP>1</SP>) 3-m CY m M<SP>11</SP>, wherein X represents halogen, alkyl, alkoxy or aralkoxy and M<SP>11</SP> represents Li, MgX (X being halogen) or another Group I to IV non-transition metal; (2) by reacting a compound LnM.M<SP>111</SP> r  with a compound (R<SP>1</SP>R<SP>2</SP>R<SP>3</SP>M<SP>1</SP>) 3-m CY m X, wherein X represents halogen and M<SP>111</SP> represents Na, K, Li or MgX; (3) by reacting a compound L n M with a compound (R<SP>1</SP>R<SP>2</SP>R<SP>3</SP>M<SP>1</SP>) 3-m CY m X<SP>1</SP>, wherein X<SP>1</SP> represents halogen or (R<SP>1</SP>R<SP>2</SP>R<SP>3</SP>M<SP>1</SP>) 3-m CY m ; (4) by reacting a compound L n M(CY m X 3-m ) r  with a compound M<SP>1111</SP>M<SP>1</SP>R<SP>1</SP>R<SP>2</SP>R<SP>3</SP>, wherein X represents halogen and M<SP>1111</SP> represents Na, K, Li, ¢Mg or ¢Hg; (5) by replacing one or more of several [CY m (MR<SP>1</SP>R<SP>2</SP>R<SP>3</SP>) 3-m ] ligands by other ligands, e.g. by reaction with alcohols, silanols, nitric acid, carboxylic acids, halogens, hydrogen halides, alkali metal halides, magnesium and alkaline earth metals; (6) by exchanging L-type ligands with other L-type ligands; (7) by subtraction or addition of other L-type ligands, e.g. by means of a metathetical exchange reaction such as Examples describe the preparation of tetrakis- (trimethylsilylmethyl) titanium, bis - (cyclopentadienyl) bis - (trimethylsilylmethyl) titanium, bis - (cyclopentadienyl) bis - (trimethylsilylmethyl) zirconium, tetrakis - (trimethylsilylmethyl) zirconium, chlorobis-(cyclopentadienyl) trimethylsilylmethyl zirconium, bis- (cyclopentadienyl) bis - (trimethylsilylmethylhafnium, trimethylsilylmethyl (#-cyclopentadienyltricarbonyl) molybdenum, trimethylsilylmethyl (# - cyclopentadienyltricarbonyl) tungsten, dimethylphenylsilylmethyl (# - cyclopentadienyltricarbonyl) tungsten, trimethylsilylmethyl (triphenylphosphine) rhodium, triphenylphosphine - # - cyclopentadienyl (trimethylsilylmethyl) nickel, bis - (diphenyltrimethylsilylmethyl) nickel, bis-(tris-(trimethylsilyl) methyl) nickel, cis - bis - (dimethylphenylphosphine) bis - (trimethylsilylmethyl) platinum, cis - bis - (triethylphosphine) bis - (trimethylsilylmethyl) platinum, cis - bis - (methyldiphenylphosphine) - bis - (trimethylsilylmethyl) platinum, cis - bis - (triphenylphosphine) bis- (trimethylsilylmethyl) platinum, cis - chlorobis - (triphenylphosphine) trimethylsilylmethyl platinum, cis- and trans - chlorobis - (dimethylphenylphosphine) trimethylsilylmethyl platinum, cis - chlorobis - (triethylphosphine) trimethylsilylmethyl platinum, cis- and transbromobis - (dimethylphenylphosphine) trimethylsilylmethyl platinum, cis - iodobis- (triphenylphosphine) trimethylsilylmethyl platinum, cis - iodobis - (triphenylphosphine) trimethylsilylphenylmethyl platinum, cis-bis-(dimethylphenylphosphine) trimethylsilylmethyl (nitrato) platinum, cis - chlorobis-(methyldiphenylphosphine) trimethylsilylmethyl platinum, cis - bromobis - (methyldiphenylphosphine) trimethylsilylmethyl platinum, cis - bromobis - (triphenylphosphine) trimethylsilylmethyl platinum and cis-bromobis - (triethylphosphine) trimethylsilylmethyl platinum. Uses.-The products are used as catalyst in the vinylic polymerization, isomerization and oligomerization of olefins and also in hydrogenation, dehydrogenation, hydroformylation and hydrosilylation reactions.