Syntheses and Crystal Structures of Ruthenium and Rhodium Olefin Complexes Containing GaCp

The reactivity of olefin containing complexes of the d8 metals Ru0 and RhI toward GaCp* and AlCp* is presented. [Ru(η4-butadiene)(PPh3)3] reacts with GaCp* to give the substitution product [Ru(η4-butadiene)(PPh3)2(GaCp*)] (1), which proved to be stable in the presence of GaCp* even under hydrogenolytic conditions. In contrast, the bis-styrene complex [Ru(PPh3)2(styrene)2] undergoes full substitution of the olefin ligands to give [Ru(PPh3)2(GaCp*)3] (2), whereas reaction of [Ru(η2,η2-COD)(η6-COT)] (COD = 1,5-cyclooctadiene, C8H12, COT = 1,3,5-cyclooctatriene, C8H10) and GaCp* leads to [Ru(η2,η2-COD)(GaCp*)3] (3) under mild hydrogenolytic conditions. Analogously, the RhI compounds [{Rh(η2,η2-NBD)(PCy3)2}{BArF}] (NBD = norbornadiene) and [{Rh(η2,η2-COD)2}{BArF}] ({BArF}= B{[C6H3(CF3)2]4) yield the complexes [{Rh(η2,η2-NBD)(PCy3)(GaCp*)2}{BArF}] (4), [{Rh(η2,η2-COD)(GaCp*)3}{BArF}] (5), and [{Rh(η2,η2-COD)(AlCp*)3}{BArF]}] (6) upon reaction with the appropriate ECp* ligand (E = Al, Ga). All new complexes have been characterized by means of 1H and 13C NMR spectroscopy and elemental analysis, as well as X-ray single crystal structure analysis in the case of 1−5.