Insights into the Schrock 'chop-chop' reaction gained from density functional theory and preparation and structure of W2(mu-PhCCPh)(SC6H4-2-Me)6.
Computations employing density functional theory on the reactions between ethyne and the model compounds (HE)3M identical to M(EH)3, where M = Mo and W and E = O and S, predict that the alkyne adducts M2(mu-C2H2)(EH)6 are thermodynamically favored with respect to the metathesis products HC identical to M(EH)3 except when M = W and E = O; the reaction between (tBuO)3 W identical to CPh and 2-MeC6H4SH (> 3 equiv.) yields W2(mu-PhCCPh)(SC6H4-2-Me)6 consistent with expectations based on the calculations.
Chisholm
Malcolm H
MH
Department of Chemistry, Ohio State University, 100 W. 18th Avenue, Columbus, Ohio 43210, USA. chisholm@chemistry.ohio-state.edu
Davidson
Ernest R
ER
Pink
Maren
M
Quinlan
Kristine B
KB