Mechanism of formation of platinum (0) complexes containing silicon-vinyl ligands

Journal Article · Mon May 01 00:00:00 EDT 1995 · Organometallics

DOI:https://doi.org/10.1021/om00005a021· OSTI ID:50795

Lewis, L N; Colborn, R E; Grade, H; Bryant, Jr, G L; Sumpter, C A ^[1]; Scott, R A ^[2]

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1. GE Corporate Research and Development Center, Schenectady, NY (United States)
2. Univ. of Georgia, Athens, GA (United States)

Reactions are described in detail between H{sub 2}PtCl{sub 6} and vinyl-silicon-containing compounds such as 1,3-divinyltetramethyldisiloxane (M{sup vi}M{sup vi}) and divinyldimethylsilane ((CH{sub 3}){sub 2}Si(CH=CH{sub 2}){sub 2}). The structures of the platinum and silicon products were examined from these reactions with M{sup vi}M{sup vi} and 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane (D{sub 4}{sup vi}). The platinum products were all Pt(0)-olefin complexes. The reaction of chloroplatinic acid with M{sup vi}M{sup vi} gave a mixture of platinum complexes containing M{sup vi}D{sub x}M{sup vi} ligands (1; x = 0-11). Some complexes are polynuclear with bridging ligands and no metal-metal bonds, such as Pt{sub 2}-(M{sup vi}M{sup vi}){sub 3} (2). The conversion of Pt(IV) complexes to Pt(0) species resulted in the net conversion of a silicon-vinyl group to a silicon-oxygen group. The reaction of H{sub 2}PtCl{sub 6} with (CH{sub 3}){sub 2}Si(CH=CH{sub 2}){sub 2} ligand gave both a Pt(0) (4) and Pt(II) (5) product. The structure of 4 was determined by spectroscopic analysis to be a Pt(0)-olefin complex. The structures of 4 and 5 were further confirmed by preparation of chemical derivatives with P(C{sub 6}H{sub 5}){sub 3}, which formed known platinum phosphine compounds. Compound 4 converted to compound 5 by reaction with HCl. 54 refs., 7 figs., 7 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 50795
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 5 Vol. 14; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ABSORPTION SPECTRA
BOND ANGLE
BOND LENGTHS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
ETHYLENE
EXPERIMENTAL DATA
INORGANIC ACIDS
LIGANDS
MASS SPECTRA
NMR SPECTRA
NUMERICAL DATA
PLATINUM COMPLEXES
PLATINUM COMPOUNDS
SILANES
SILICON COMPOUNDS
SILOXANES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
VINYL RADICALS