Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium-Indium Bonds.

The hydride complex [Ru(IPr)2 (CO)H][BArF4 ], 1, reacts with InMe3 with loss of CH4 to form [Ru(IPr)2 (CO)(InMe)(Me)][BArF4 ], 4, featuring an unsupported Ru-In bond with unsaturated Ru and In centres. 4 reacts with H2 to give [Ru(IPr)2 (CO)(η2 -H2 )(InMe)(H)][BArF4 ], 5, while CO induces formation of the indyl complex [Ru(IPr)2 (CO)3 (InMe2 )][BArF4 ], 7. These observations highlight the ability of Me to shuttle between Ru and In centres and are supported by DFT calculations on the mechanism of formation of 4 and its reactions with H2 and CO. An analysis of Ru-In bonding in these species is also presented. Reaction of 1 with GaMe3 also involves CH4 loss but, in contrast to its In congener, sees IPr transfer from Ru to Ga to give a gallyl complex featuring an η6 interaction of one aryl substituent with Ru.