Development of New Catalytic Reactions Promoted by Iron Complexes

摘要

Transition metal complexes have attracted considerable attentions because they show a variety of structures, reactivities, and properties. We have focused on the reactivity, especially the catalytic activity of iron complexes. An iron is an attractive precious metal surrogate because of its high natural abundance, low cost, and environmental compatibility. In this account, three topics concerning iron catalyst were selected from our results obtained. (i) An iron silyl complex can cleave a strong bond selectively. C-CN bonds in organonitriles, N-CN bonds in cyanamides, O-CN bonds in cyanates, Si-CN bonds in silylnitriles, C=O double bonds in formamides, and C=S double bonds in thioformamides were selectively cleaved with remaining weaker bonds intact. Silyl migration from iron serves as a trigger of the selective strong bond cleavage. (ii) Olefin hydrosilylation took place effectively in the presence of iron complex catalyst. Our system showed the highest catalytic activity among iron complex catalysts. In addition, an unprecedented hydrosilylation reaction was achieved by an iron complex catalyst. (iii) Catalytic double hydrophosphination promoted by an iron complex was developed. In this reaction, the starting phosphine and the diphosphine product did not serve as catalyst poison in the iron catalytic system.