Mono- and binuclear bipyridyl derivatives of the Mo(eta(3)-C3H5)(CO)(2) fragment: structural studies and fluxionality in solution
authors Costa, PMFJ; Mora, M; Calhorda, MJ; Felix, V; Ferreira, P; Drew, MGB; Wadepohl, H
nationality International
journal JOURNAL OF ORGANOMETALLIC CHEMISTRY
author keywords molybdenum; allyl complexes; crystal structures; bipyridyl complexes; binuclear complexes
keywords CATALYZED ALLYLIC ALKYLATIONS; TUNGSTEN COMPLEXES; DYNAMIC-BEHAVIOR; MOLYBDENUM; LIGANDS
abstract New mono- and binuclear complexes of the Mo(eta(3)-C3H5)(CO)(2) fragment, containing bipyridyl ligands (2,2'-bpy, 4,4'-Me-2-2,2'-bpy) as chelates, and mono- (4-CNpy, 4-Mepy, NCMe, Br) or bidentate nitrogen ligands (4,4'-bpy, bipyridylethylene, pyrazine) as terminal or bridging ligands, respectively, were prepared. The binuclear complex [{Mo(eta(3)-C3H5)(CO)(2)(2,2'-bpy)}(2)(mu-4,4'-bpy)][PF6](2) (2) was shown by X-ray diffraction to assemble in the crystal forming large channels with a rectangular section. A longer bridge, such as bipyridylethylene, led to a different structure (3). 4-CNpy behaved as monodentate ligand (4), coordinating through the pyridine nitrogen as a terminal ligand. NMR spectroscopy studies showed that the complexes exhibited a fluxional behavior in solution, the endo and exo forms of the more symmetrical equatorial isomers being usually present and interconverting in solution. The solid state structures of the complexes revealed a preference for the more symmetrical equatorial isomer, with the two chelate ligands in trans positions in the binuclear species. The rings tended to become parallel in the organized crystal. (C) 2003 Elsevier B.V. All rights reserved.
publisher ELSEVIER SCIENCE SA
issn 0022-328X
year published 2003
volume 687
issue 1
beginning page 57
ending page 68
digital object identifier (doi) 10.1016/j.jorganchem.2003.08.004
web of science category Chemistry, Inorganic & Nuclear; Chemistry, Organic
subject category Chemistry
unique article identifier WOS:000186691700008
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