Insights into the Schrock ‘chop-chop’ reaction gained from density functional theory and preparation and structure of W2(μ-PhCCPh)(SC6H4-2-Me)6

Abstract

Computations employing density functional theory on the reactions between ethyne and the model compounds (HE)₃MM(EH)₃, where M = Mo and W and E = O and S, predict that the alkyne adducts M₂(μ-C₂H₂)(EH)₆ are thermodynamically favored with respect to the metathesis products HCM(EH)₃ except when M = W and E = O; the reaction between (^tBuO)₃WCPh and 2-MeC₆H₄SH (>3 equiv.) yields W₂(μ-PhCCPh)(SC₆H₄-2-Me)₆ consistent with expectations based on the calculations.