Abstract
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.