1. Catalytic Hydrogenation of Benzonitrile by Triruthenium Clusters: Consecutive Transformations of Benzonitrile on the Face of a Ru3 Plane
- Author
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Takashi Kawashima, Yuta Takahashi, Hiroharu Suzuki, Akira Sawano, Toshiro Takao, Sachie Horikoshi, and Sachio Asano
- Subjects
Nitrile ,010405 organic chemistry ,Organic Chemistry ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,0104 chemical sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,Benzonitrile ,Benzylamine ,chemistry ,Physical and Theoretical Chemistry ,Selectivity ,Catalytic hydrogenation - Abstract
Reactions of the triruthenium clusters {Cp*Ru(μ-H)}3(μ3-H)2 (1) and (Cp*Ru)3(μ3-H)(μ-H)2(μ-CO) (12) (Cp* = η5-C5Me5) with benzonitrile were investigated in relation to the selective hydrogenation of benzonitrile to benzylamine. Benzonitrile undergoes consecutive transformations into μ3-η2:η2(⊥)-nitrile, μ3-η2:η2(⊥)-imidoyl, μ3-η2(∥)-imidoyl, μ3-η2-alkylideneamido, μ3-imido, and μ-amido ligands on the Ru3 plane accompanied by the uptake of dihydrogen. The reactions are analogues of nitrile hydrogenation on a metal surface. The complexes are structural models of chemisorbed species and catalyze the hydrogenation of benzonitrile. Complex 1 catalyzes benzonitrile hydrogenation without additives but exhibits only moderate selectivity toward benzylamine. Although the μ3-benzylimido complex {Cp*Ru(μ-H)}3(μ3-NCH2Ph) (4) was obtained by reaction of 1 with benzonitrile, it was readily transformed into to the μ3-imidoyl complexes (Cp*Ru)3(μ-H)2{μ3-η2:η2(⊥)-PhCNH} (3) and (Cp*Ru)3(H)4{μ3-η2(∥∥)-PhCNH} (4), which are ...
- Published
- 2018