Synthesis, Structure, and Reactivity of Ruthenium‐Indane Complexes with diphosphine ligand

Ruthenium‐indane complex, fac‐ [Ru(NCMe) 3 (CO) 2 (InCl 3 )] 1Cl reacted with 0.5 equiv. of dppe/dppp to afford dinuclear ruthenium‐indane complexes linked by diphosphine ligand, [{Ru(NCMe) 2 (CO) 2 (InCl 3 )} 2 {μ 2 ‐Ph 2 P(CH 2 ) n PPh 2 }] (n=2: 3 , 3: 4 ). On the other hand, the reaction of fac‐ [Ru(NCMe) 3 (CO) 2 (InCl 3 )] 1Cl with 1 equiv. of dppp afforded the corresponding chelate ruthenium(0) indane complex, [Ru(NCMe)(CO) 2 (InCl 3 )(dppp)] 5 . In the case of dppm, a chelate complex [Ru(NCMe)(CO) 2 (InCl 3 )(dppm)] 6 was formed via the dinuclear Ru complex [{Ru(NCMe) 2 (CO) 2 (InCl 3 )} 2 (μ 2 ‐dppm)]. Complexes 1Cl , 5 , and 6 showed a catalytic activity for double‐hydrosilylation of MeCN. Complexes 3 – 6 were fully characterized using NMR measurements, elemental analyses, and the structures of 1Cl , 3 , 5 , and 6 were determined by X‐ray crystallography.