Toshiaki Kobayashi

Chemistry of organosilicon compounds

Abstract Two new 1,2-disilacyclobutenes have been prepared by the reaction of tetramethyldisilene with acetylenes. Several reactions of these new 1,2-disilacyclobutenes including oxidation, silylene insertion, iron carbonyl insertion, and addition to acetylenes and dienes are reported.

Chemistry of organosilicon compounds 118. Novel ring contraction reaction of (η4-1,2-disilacyclohexadiene)iron tricarbonyls

Abstract 1,1,2,2-Dimethyl-3,6-diphenyl-1,2-disilacyclohexadiene reacts with iron pentacarbonyl or diiron nonacarbonyl to give the corresponding (diene)iron tricarbonyl complex which undergoes novel ring contraction reaction to (η 4 -1,1-dimethyl-2,5-diphenyl-1-silacyclopentadiene)iron tricarbonyl on thermolysis at 160°C. Similar results were observed with 1,1,2,2-tetramethyl-3,4,5,6-tetraphenyl-1,2-disilacyclohexadiene.

Preparation, reactions and stereochemistry at silicon of (2,3,4,5-tetraphenyl-1-silacyclopentadiene)iron tricarbonyls☆

Abstract Twelve derivatives of (2,3,4,5-tetraphenyl-1-silacyclopentadiene)iron tricarbonyls were prepared. These complexes undergo a variety of substitution at silicon. The exo leaving groups showed enhanced reactivity in such reactions. The stereochemistry of substitution also differs significantly from that established for optically active silanes.

Chemistry of organosilicon compounds : CXLII. 29Si nmr spectra of some iron and ruthenium complexes containing silicon. Reassignment of the structures of the complexes obtained by the reaction vinyldisilanes and nonacarbonyldiiron

Abstract 29 Si NMR studies on several iron and ruthenium carbonyl complexes containing silicon revealed that the complexes obtained from vinyldisilanes and nonacarbonyldiiron previously reported to be (η 3 -1-silapropenyl)tricarbon: iron compounds really are (η 2 -vinyldisilane)tetracarbonyliron complexes.

Chemistry of organosilicon compounds : LXXXVIII. Mass spectroscopy of organosilicon compounds. Part 2. Methoxymethyldisilanes

Abstract Mass spectra of various methoxymethyldisilanes were examined in detail. Characteristic features of the spectra of these compounds are: (a) the fission of the Si—C bond occurs more readily than that of the Siue5f8Si bond; (b) the methoxy group is eliminated as formaldehyde; (c) the silicon analog of an acyl cation is formed from the [ M ue5f815] + ion; (d) the 1,2-shift of the methoxy group is characteristic in the fragmentation process.