Heterobimetallic ruthenium–zinc complexes with bulky N-heterocyclic carbenes: syntheses, structures and reactivity

The ruthenium–zinc heterobimetallic complexes, [Ru(IPr)2(CO)ZnMe][BArF4] (7), [Ru(IBiox6)2(CO)(THF)ZnMe][BArF4] (12) and [Ru(IMes)′(PPh3)(CO)ZnMe] (15), have been prepared by reaction of ZnMe2 with the ruthenium N-heterocyclic carbene complexes [Ru(IPr)2(CO)H][BArF4] (1), [Ru(IBiox6)2(CO)(THF)H][BArF4] (11) and [Ru(IMes)(PPh3)(CO)HCl] respectively. 7 shows clean reactivity towards H2, yielding [Ru(IPr)2(CO)(η2-H2)(H)2ZnMe][BArF4] (8), which undergoes loss of the coordinated dihydrogen ligand upon application of vacuum to form [Ru(IPr)2(CO)(H)2ZnMe][BArF4] (9). In contrast, addition of H2 to 12 gave only a mixture of products. The tetramethyl IBiox complex [Ru(IBioxMe4)2(CO)(THF)H][BArF4] (14) failed to give any isolable Ru–Zn containing species upon reaction with ZnMe2. The cyclometallated NHC complex [Ru(IMes)′(PPh3)(CO)ZnMe] (15) added H2 across the Ru–Zn bond both in solution and in the solid-state to afford [Ru(IMes)′(PPh3)(CO)(H)2ZnMe] (17), with retention of the cyclometallation.We thank the EU (Marie Curie Individual Fellowships to ME-V (700189 H2020-MSCA-IF 2015) and FMM (792674 H2020-MSCA-IF 2017)) and EPSRC (grant EP/J009962/1; IMR) for financial support. VV-I thanks MINECO/FEDER (CTQ2017-83421-P) and Gobierno de Aragón (GA/FEDER, Inorganic Molecular Architecture Group E08_17R) for financial support and MINECO/FEDER for a FPI fellowshipPeer reviewe