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 +

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.