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Lithium Di-­‐ and Trimethyl Dimolybdenum(II) Complexes with Mo-­‐Mo Quadruple Bonds and Bridging Methyl Groups

AuthorsCurado, Natalia ; Carrasco, Mario ; Álvarez, Eleuterio ; Maya, Celia ; Peloso, Riccardo ; Rodríguez, Amor ; López-Serrano, Joaquín ; Carmona, Ernesto
KeywordsBridging methyl groups
Multiple bonds
NMR spectroscopy
Competitional studies
Issue Date2015
PublisherAmerican Chemical Society
CitationJournal of the American Chemical Society, 137 (38), pp 12378–12387 (2015)
AbstractNew dimolybdenum complexes of composition [Mo2{μ-Me}2Li(S)}(μ- X)(μ-N^N)2] (3a−3c), where S = THF or Et2O and N^N represents a bidentate aminopyridinate or amidinate ligand that bridges the quadruply bonded molybdenum atoms, were prepared from the reaction of the appropriate [Mo2{μ-O2CMe}2(μ-N^N)2] precursors and LiMe. For complex 3a, X = MeCO2, while in 3b and 3c, X = Me. Solution NMR studies in C6D6 solvent support formulation of the complexes as contact ion pairs with weak agostic Mo−CH3···Li interactions, which were also evidenced by X-ray crystallography in the solid-state structures of the molecules of 3a and 3b. Samples of 3c enriched in 13C (99%) at the metal-bonded methyl sites were also prepared and investigated by NMR spectroscopy employing C6D6 and THF-d8 solvents. Crystallization of 3c from toluene:tetrahydrofuran mixtures provided single crystals of the solvent separated ion pair complex [Li(THF)4] [Mo2(Me)2(μ-Me){μ-HC(NDipp)2}2] (4c), where Dipp stands for 2,6-iPr2C6H3. A computational analysis of the Mo2(μ-Me)2Li core of complexes 3a and 3b has been developed, which is consistent with a small but non-negligible electron-density sharing between the C and Li atoms of the mainly ionic CH3···Li interactions.
Publisher version (URL)http://dx.doi.org/10.1021/jacs.5b07899
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