Notable Catalytic Activity of Transition Metal Thiolate Complexes against Hydrosilylation and Hydroboration of Carbon-Heteroatom Bonds.

Chemists tend to use transition metal hydride complexes rather than thiolate complexes to catalyse chemical transformations because the hydride complexes possess diverse catalytic reactivity, although most of them are air/moisture-sensitive and difficult to prepare. By comparing the catalytic performances of pincer ligated group 10 metal thiolate and hydride complexes in catalysing the hydroboration and hydrosilylation of C=O and C=N bonds, we demonstrate in this review that transition metal thiolate complexes are much better catalysts than the corresponding hydride complexes in catalysing this type of reactions. Many hydroboration and hydrosilylation reactions catalysed by pincer ligated group 10 metal hydride complexes can also be catalysed by the corresponding thiolate complexes and the thiolate systems are far more active. Therefore, the applications of transition metal thiolate complexes in the catalytic hydroboration and hydrosilylation of unsaturated carbon-heteroatom bonds deserve special attention in future work.