An Anionic Ruthenium Dihydride [Cp*(iPr2MeP)RuH2]− and Its Conversion to Heterobimetallic Ru(μ-H)2M (M = Ir or Cu) Complexes

A novel dihydridoruthenate, [(solv)Na][Cp*(iPr2MeP)RuH2] (2; solv = THF or OEt2), was synthesized from Cp*(iPr2MeP)RuCl (1) and sodium triethylborohydride. Compound 2 was used to generate “Cp*(iPr2MeP)RuH” equivalents by salt metathesis with 1, which resonance Raman spectroscopy indicates is a mixture of the terminal dinitrogen complex, Cp*(iPr2MeP)RuH(N2) (4), and diastereomers of the bridging dinitrogen complex [Cp*(iPr2MeP)RuH]2(μ-N2) (meso, 5, and a pair of enantiomers, 6). Compound 2 also reacted with the late transition metal chloride complexes [(COD)IrCl]2 and (IPr)CuCl [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene] to form hydride-bridged heterobimetallic complexes Cp*(iPr2MeP)Ru(μ-H)2Ir(COD) (7) and Cp*(iPr2MeP)Ru(μ-H)2Cu(IPr) (8), respectively, that feature weakened Ru–H interactions relative to those of 2.