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An Unsaturated Four-Coordinate Dimethyl Dimolybdenum Complex with a Molybdenum–Molybdenum Quadruple Bond

AutorCurado, Natalia ; Carrasco, Mario ; Campos, Jesús ; Maya, Celia ; Rodríguez, Amor ; Ruiz, E.; Álvarez, Santiago; Carmona, Ernesto
Fecha de publicación2017
EditorJohn Wiley & Sons
CitaciónChemistry - A European Journal 23: 194- 205 (2017)
ResumenWe describe the synthesis and the molecular and electronic structures of the complex [MoMe{μ-HC(NDipp)}] (2; Dipp=2,6-iPrCH), which contains a dimetallic core with an Mo–Mo quadruple bond and features uncommon four-coordinate geometry and has a fourteen-electron count for each molybdenum atom. The coordination polyhedron approaches a square pyramid, with one of the molybdenum atoms nearly co-planar with the basal square plane, in which the trans coordination position with respect to the Mo−Me bond is vacant. The other three sites are occupied by two trans nitrogen atoms of different amidinate ligands and the methyl group. The second Mo atom occupies the apex of the pyramid and forms an Mo–Mo bond of length 2.080(1) Å, consistent with a quadruple bond. Compound 2 reacts with tetrahydrofuran (THF) and trimethylphosphine to yield the mono-adducts [MoMe(μ-Me){μ-HC(NDipp)}(L)] (3⋅THF and 3⋅PMe, respectively) with one terminal and one bridging methyl group. In contrast, 4-dimethylaminopyridine (dmap) forms the bis-adduct [MoMe{μ-HC(NDipp)}(dmap)] (4), with terminally coordinated methyl groups. Hydrogenolysis of complex 2 leads to the bis(hydride) [MoH{μ-HC(NDipp)}(thf)] (5⋅THF) with elimination of CH. Computational, kinetic, and mechanistic studies, which included the use of D and of complex 2 labelled with C (99 %) at the Mo–CH sites, supported the intermediacy of a methyl-hydride reactive species. A computational DFT analysis of the terminal and bridging coordination of the methyl groups to the Mo≣Mo core is also reported.
URIhttp://hdl.handle.net/10261/148592
DOI10.1002/chem.201604618
Identificadoresdoi: 10.1002/chem.201604618
issn: 1521-3765
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