Iron disilyl dicarbonyl complex 1, in which two H-Si moieties of the 1,2-bis(dimethylsilyl)benzene ligand were coordinated to the iron center in an η(2)-(H-Si) fashion, was synthesized by the reaction of (η(4)-C6H8)Fe(CO)3 with 2 equiv. of 1,2-bis(dimethylsilyl)benzene under photo-irradiation. Complex 1 demonstrated high catalytic activity toward the hydrogenation of alkenes, the hydrosilylation of alkenes and the reduction of carbonyl compounds.

The appropriate design of a ligand (L) in IrCl­(CO)­(L)2 (4) realized the efficient synthesis of π-conjugated enamines possessing hole-transport properties. The iridium complex with electron-withdrawing phosphorus ligands catalyzed the hydrosilylation of amides to the corresponding silylhemiaminals, which were transformed to the enamines by heat or by treatment with acids. High catalytic efficiency (TON > 10,000) was achieved, which made it possible for the residual iridium in the enamine product to be below 20 ppb.