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

Oligosilylanions and their Reactions with Zirconocene and Hafnocene Dichlorides

“…Reactions of silyl potassium compounds were expected to proceed analogously to the reactions with silyl lithium compounds described by Tilley et al some years ago [5,6] (Scheme 2).…”

A New and Easy Route to Polysilanylpotassium Compounds

“…Syntheses of an acylsilane (5), [15] and of the known to a disilene. [12] The polysilyl anions 10 and 11 are candidates for experizirconocene hypersilyl chloride (6), [16] can be achieved in a straightforward manner. The reaction of 1a with 1,2-dibro-ments in which the polysilyl moiety is required to be of increased size compared to the "hypersilyl" unit in order to moethane at Ϫ78°C proceeds in an analogous manner to that of the corresponding lithium compound 1, and yields fulfill its stabilizing function.…”

Acyl Silanes

“…Following several years of speculation 5,46 , Ireland and Norbeck achieved strong evidence for the formation of formyl trimethylsilane using a trap with a Wittig reagent following Swern oxidation 47 of trimethylsilyl methanol (vide infra, Section III.A.5) 48 . Formyl trimethylsilane was subsequently identified by Tilley using NMR spectroscopy as the product of reaction of the zirconium Á 2 -sila-acyl complex (Á 5 -C 5 H 5 ) 2 Zr(Á 2 -COSiMe 3 )Cl (1) with hydrochloric acid 49 , and has recently been prepared by in situ reaction of 1,1-dimethylsilene with formaldehyde; the formyl silane rearranged quantitatively to 2,2-dimethyl-2-silapropanal within a few minutes (Scheme 1) 50 . Tilley was later able to prepare, isolate and characterize the first stable formyl silane, formyl tris(trimethylsilyl)silane, from the zirconium Á 2 -sila-acyl complex (2) 51 by treatment with anhydrous hydrogen chloride at 78°C in toluene solution.…”