1624848-19-6Relevant academic research and scientific papers
Experimental and theoretical studies on arene-bridged metal-metal-bonded dimolybdenum complexes
Carrasco, Mario,Curado, Natalia,Alvarez, Eleuterio,Maya, Celia,Peloso, Riccardo,Poveda, Manuel L.,Rodriguez, Amor,Ruiz, Eliseo,Alvarez, Santiago,Carmona, Ernesto
, p. 6092 - 6102 (2014)
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 C 6H5OMe, p-C6H4Me2, C 6H5F, 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. Quintuply bound [Mo2{HC(N-2,6-iPr 2C6H3)2}2(arene)] complexes (arene=C6H6, C6H5Me, C6H5OMe, p-C6H4Me2, C6H5F, and p-C6H4F2 and Dipp=2,6-iPr2C6H3) have been prepared and structurally characterized by experimental and theoretical methods (see figure). Coordination of the arene to the quintuple MoI-MoI bond results in an effective metal-metal bond order substantially lower than five as a consequence of a strong electronic interaction between δ and δ* dimetal orbitals and the π and π* orbitals of the arene.
