Mechanism of protonation of side-on bonded vinylidene complexes; structural evidence for the formation of a cationic di-molybdenum complex containing an asymmetrically bridged allyl ligand

Abstract
α-Protonation of side-on bonded vinylidenes is indicated by the observations that reaction of CF3CO2D with [Mo2{µ-σ,η2(4e)CCH2}(CO)4(η-C5H5)2] affords [Mo2{σ-OC(O)CF3}(η-CDCH2)(CO)4(η-C5H5)2], whereas, CF3CO2H and [Mo2{µ-σ, η2(4e)CCD2}(CO)4(η-C5H5)2] gives [Mo2{σ-OC(O)CF3}(µ-CHCD2)-(CO)4(η-C5H5)2]; in contrast, reaction of HBF4·Et2O with [Mo2{µ-σ,η2(4e)CCMe2}(CO)4(η-C5H5)2] leads to loss of CO and formation of the Mo2 triple bonded cation [Mo2(µ-η3-2-MeC3 H4)(CO)3(η-C5H 5)2][BF4], an asymmetrically bridged allyl complex which is also formed on protonation of [Mo2{µ-σ:η3-CHC (Me)CH2}(CO)4(η-C5H5)2].

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