Abstract
The mechanism of conversion of terminal alkynes RC CH to coordinated carbyne Os CCH 2R by Os(H) 2ClXL 2 (L = P i Pr 3) has been studied for X = OTf and BAr F 4 (Ar F = 3,5-di(CF 3) 2(C 6H 3). Ready loss of these X makes possible detection of η 2-RCCH (4-electron donor) and CH(CH 2R) intermediates, and D-labeling (RCCD) gives OsDClX(CCH 2R)L 2. The energy of various intermediates, including the only experimentally unobserved one, η 2-vinyl, was evaluated with DFT(PBE) calculations.
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