Syntheses and crystal structures of ruthenium and rhodium olefin complexes containing GaCp

The reactivity of olefin containing complexes of the d⁸ metals Ru⁰ and Rh¹ toward GaCp^* and AlCp ^* is presented. [Ru(η⁴-butadiene)(PPh ₃)₃] reacts with GaCp^* to give the substitution product [Ru(η-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(PPh ₃)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 Rh ¹ compounds [{Rh(η²,η²-NBD)(PCy ₃)₂}{BAr^F}] (NBD = norbornadiene) and [{Rh(η²,η²-COD)₂}{BAr^F}] ({BAr^F}= B{[C₆H₃(CF₃) ₂]₄) yield the complexes [{Rh(η², η²-NBD)(PCy₃)(GaCp^*) ₂}{BAr^F}] (4), [{Rh(η²,η²- COD)(GaCp^*)₃}{BAr^F}] (5), and [{Rh(η²,η²-COD)(AICp^*) ₃}{BAr^F]}] (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.