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Interconversion of Quadruply and Quintuply Bonded Molybdenum Complexes by Reductive Elimination and Oxidative Addition of Dihydrogen


Mario Carrasco, Natalia Curado, Celia Maya, Riccardo Peloso, Amor Rodríguez, Eliseo Ruiz, Santiago Álvarez, Ernesto Carmona Angew. Chem. Int. Ed. 2013, Vol. 52, 3227-3231

A series of dimolybdenum dihydride complexes supported by amidinate ligands and featuring a Mo—Mo quadruple bond, MoII2, has been prepared and characterized by NMR spectroscopy and x-ray crystallography. UV irradiation (365 nm) of one of these complexes, namely the bis(tetrahydrofuran) adduct [Mo2(H)2{HC(N-2,6-Pri2C6H3)2}2(THF)2], 2, induces reductive elimination of H2 with formation of the known MoI2 complex [Mo2{HC(N-2,6-Pri2C6H3)2}2], 3, that exhibits fivefold Mo—Mo bonding. As the latter compound undergoes readily oxidative addition of H2 to restore the starting bis(hydride) derivative, 2, this reactivity demonstrates that Mo2 complexes with quadruple and quintuple M—M bonds can interconvert by means of these fundamental reactions of the dihydrogen molecule. Performing the UV irradiation of 2 in the aromatic hydrocarbon solvents benzene and toluene leads to novel arene adducts of composition [Mo2{HC(N-2,6-Pri2C6H3)2}2(C6H5R)], 4·C6H6 and 4·C6H5CH3, respectively, in which the aromatic hydrocarbon bridges the molybdenum atoms of the electron-rich MoI2 unit, coordinating to each in a μ2 fashion. Density functional theory calculations indicate that arene coordination to the Mo2 unit induces a substantial electronic reorganization of both the metal δ and arene π systems, leading to an effective reduction of the Mo—Mo and C—C bond orders.


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