Mono- and binuclear bipyridyl derivatives of the Mo(η3-C 3H5)(CO)2 fragment: Structural studies and fluxionality in solution

Pedro Da Costa, Márcia Mora, Maria José Calhorda, Vitor Félix, Paula Ferreira, Michael G.B. Drew, Hubert Wadepohl

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26 Scopus citations

Abstract

New mono- and binuclear complexes of the Mo(η3-C 3H5)(CO)2 fragment, containing bipyridyl ligands (2,2′-bpy, 4,4′-Me2-2, 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(η3-C3H5) (CO)2(2,2′-bpy)}2(μ-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.

Original languageEnglish (US)
Pages (from-to)57-68
Number of pages12
JournalJournal of Organometallic Chemistry
Volume687
Issue number1
DOIs
StatePublished - Dec 1 2003

Keywords

  • Allyl complexes
  • Binuclear complexes
  • Bipyridyl complexes
  • Crystal structures
  • Molybdenum

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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