Experimental and Theoretical Studies on Arene‐Bridged Metal–Metal‐Bonded Dimolybdenum Complexes |
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| Authors: | Dr Mario Carrasco Natalia Curado Dr Eleuterio Álvarez Dr Celia Maya Dr Riccardo Peloso Prof?Dr Manuel L Poveda Dr Amor Rodríguez Prof?Dr Eliseo Ruiz Prof?Dr Santiago Álvarez Prof?Dr Ernesto Carmona |
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| Institution: | 1. Instituto de Investigaciones Químicas, Departamento de Química Inorgánica Universidad de Sevilla‐Consejo Superior de Investigaciones Científicas, Avenida Américo Vespucio 49, 41092 Sevilla (Spain), Fax: (+34)?954460565;2. Departament de Química Inorgànica and Institut de Química Teòrica i Computacional, Universitat de Barcelona, Diagonal 647, 08028 Barcelona (Spain) |
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| Abstract: | The bis(hydride) dimolybdenum complex, Mo2(H)2{HC(N‐2,6‐iPr2C6H3)2}2(thf)2], 2 , which possesses a quadruply bonded Mo2II core, undergoes light‐induced (365 nm) reductive elimination of H2 and arene coordination in benzene and toluene solutions, with formation of the MoI2 complexes Mo2{HC(N‐2,6‐iPr2C6H3)2}2(arene)], 3?C6H6 and 3?C6H5Me , respectively. The analogous C6H5OMe, p‐C6H4Me2, C6H5F, and p‐C6H4F2 derivatives have also been prepared by thermal or photochemical methods, which nevertheless employ different Mo2 complex precursors. X‐ray crystallography and solution NMR studies demonstrate that the molecule of the arene bridges the molybdenum atoms of the MoI2 core, coordinating to each in an η2 fashion. In solution, the arene rotates fast on the NMR timescale around the Mo2‐arene axis. For the substituted aromatic hydrocarbons, the NMR data are consistent with the existence of a major rotamer in which the metal atoms are coordinated to the more electron‐rich C?C bonds. |
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| Keywords: | arenes density functional calculations molybdenum multiple bonds NMR spectroscopy |
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