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The molybdenum and tungsten complexes M 2 (OR) 6 ( Mo2F6 , M = Mo, R = C(CF 3 ) 2 Me; W2F3 , M = W, R = OC(CF 3 )Me 2 ) were synthesized as bimetallic congeners of the highly active alkyne metathesis catalysts [MesC≡M{OC(CF 3 )  n  Me 3-   n  }] ( MoF6 , M = Mo, n = 2; WF3 , M = W, n = 1; Mes = 2,4,6-trimethylphenyl). The corresponding benzylidyne complex [PhC≡W{OC(CF 3 )Me 2 }] ( W   Ph   F3 ) was prepared by cleaving the W≡W bond in W2F3 with 1-phenyl-1-propyne. The catalytic alkyne metathesis activity of these metal complexes was determined in the self-metathesis, ring-closing alkyne metathesis and cross-metathesis of internal and terminal alkynes, revealing an almost equally high metathesis activity for the bimetallic tungsten complex W2F3 and the alkylidyne complex W   Ph   F3 . In contrast, Mo2F6 displayed no significant activity in alkyne metathesis.

Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex