Z-selective, catalytic internal alkyne semihydrogenation under H2/CO mixtures by a niobium(III) imido complex.

The discovery of a Nb(III)-mediated catalytic hydrogenation of internal alkynes to (Z)-alkenes that proceeds through an unprecedented mechanism is reported. The mechanistic proposal involves initial reduction of the alkyne by the Nb(III) complex (BDI)Nb(N(t)Bu)(CO)(2) to provide a Nb(V) metallacyclopropene, itself capable of σ-bond metathesis reactivity with H(2). The resulting alkenyl hydride species then undergoes reductive elimination to provide the (Z)-alkene product and regenerate a metal complex in the Nb(III) oxidation state. Support for the proposed mechanism is derived from (i) the dependence of the product selectivity on the relative concentrations of CO and H(2), (ii) the isolation of complexes closely related to those proposed to be part of the catalytic cycle, (iii) H/D crossover experiments, and (iv) DFT studies of multiple possible reaction pathways.