Reactions of carbon monoxide with trimethylsilyl and tris(trimethylsilyl)silyl derivatives of group 4 metals. Synthesis, characterization, and reactivity of silaacyl complexes

Journal Article · Wed Apr 01 04:00:00 EST 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00241a023· OSTI ID:6510033

Campion, B K; Falk, J; Tilley, T D

Their studies concerned with early transition-metal-silyl reactivity have included reactions with carbon monoxide in order to elucidate the factors involved in silyl migration to coordinated CO. The tendency of M-Si bonds in d/sup 0/ complexes to insert unsaturated substrates was expected to be greater than in previously studied complexes, since bond strengthening by metal-to-silicon ..pi..-donation cannot occur. Crystal structures of two zirconium silyl compounds indeed reveal rather long Zr-Si bonds. They report herein the preparation of zirconium and hafnium derivatives of -Si(SiMe/sub 3/)/sub 3/ and the reactions of these and other early transition-metal silyls with CO. These results include the first observation of CO insertion into a transition-metal-silicon bond and the X-ray crystal structure of the silaacyl complex Cp/sub 2/Zr(eta/sup 2/-COSiMe/sub 3/)Cl (9, Cp = eta/sup 5/-C/sub 5/H/sub 5/).

• Research Organization: Univ. of California, San Diego, La Jolla
• OSTI ID: 6510033
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:7; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COHERENT SCATTERING
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EXPERIMENTAL DATA
HAFNIUM COMPOUNDS
INFORMATION
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
SCATTERING
SILICON COMPOUNDS
SPACE GROUPS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
YIELDS
ZIRCONIUM COMPOUNDS