Abstract
AbstractThe reactions of ArX (X = Cl and Br) with [Mo(NO)(P∩P)(NCMe)3][BArF4] P∩P = 2,2′‐bis(diphenylphosphanyl)diphenyl ether (DPEphos), BArF4 = tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate at 120 °C resulted in the formation of biphenyl (through CAr–CAr reductive homocoupling) and the dinuclear halide salts [Mo2(NO)2(P∩P)2(NCMe)2(μ‐X)2][BArF4]2 (X = Cl, 1; Br, 2). Complexes 1 and 2 potentially show cisoid (1c and 2c) and transoid (1t and 2t) regioisomerism with respect to the position of the NO ligand. The crystal‐structure determinations of 1 and 2 revealed the presence of the transoid isomers 1t and 2t and MI–MI bonding in both cases. A proposed mechanism for the formation of 1t and 2t involves reductive CAr–CAr coupling to form biphenyl from two Ph–MoII centers. In addition, the complexes Mo(NO)(P∩P)(CO)2Cl (3) and [Mo(NO)(mer‐κ3‐P,P,O‐DPEphos)Cl(PR3)] (R = Me, 4; Ph, 5) were obtained through the reductions of [Mo2(NO)2(P∩P)2Cl4(μ‐Cl)2].
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