Ruthenium catalysis hydrosilylation

While platinum and rhodium are predominantly used as efficient catalysts in the hydrosilylation and cobalt group complexes are used in the reactions of silicon compounds with carbon monooxide, in the last couple of years the chemistry of ruthenium complexes has progressed significantly and plays a crucial role in catalysis of these types of processes (e.g., dehydrogenative silylation, hydrosilylation and silylformylation of alkynes, carbonylation and carbocyclisation of silicon substrates). 

One of the most confusing problems in the hydrosilylation catalysis by rhodium complexes is the influence of molecular oxygen as a cocatalyst. This is a general phenomenon and also occurs in the presence of other transition metal complexes, such as platinum and ruthenium, particularly those with CO and phosphine ligands. The concerted mechanism of hydrosilylation processes catalyzed by Wilkinson catalyst involves predissociation of the phosphine from the complex. In this respect, molecular oxygen functions as a promoter since the dissociation of phosphine occurs more readily from [RhCl(02)(PPh3)3] than from the... 

In the recent years, all new mechanistic implications on the late transition metal-catalyzed hydrosilylation of olefins reported involve ruthenium complexes as model transition metal centers of molecular catalysis (86-88). 

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