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Fe(1)‐Mediated C – H/C – C Bond Activation in Silanes. Evidence for a Degenerate Skeletal Reorganization Preceding the Unimolecular Ethylene Formation from n ‐C 7 H 15 Si(CH 3 ) 3 /Fe +
Author(s) -
Hässlbarth Alexander,
Prüsse Tilmann,
Schwarz Helmuit
Publication year - 1990
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19901230135
Subject(s) - chemistry , metallacycle , ethylene , silanes , stereochemistry , hydrogen bond , hydrogen , crystallography , reductive elimination , molecule , x ray crystallography , silane , catalysis , organic chemistry , physics , diffraction , optics
Extensive labeling studies permit to unravel the mechanisms by which bare Fe + activates C–H and C–C bonds of n ‐heptyltrimethylsilane in the gas phase. While the neutral products C 3 H 8 , C 5 H 12 , Si(CH 3 ) 4 , and Si(CH 3 ) 3 C 2 5 are due to an initial insertion of Fe + into various C–C bonds of the n ‐heptyl chain, followed by β‐hydrogen transfer and reductive elimination of the neutrals, molecular hydrogen and HSi(CH 3 ) 3 ar suggested to result from initial activation of specific C–H bonds. The formation of C 2 H 4 is preceded by a skeletal rearrangement of the heptyl chain, rendering C‐1/C‐4 and C‐2/C‐3 equivalent; a metallacycle 10 is suggested as an intermediate.