AN UNUSUAL COMPLEX DERIVED FROM MOCL3(THF)3 AND AGBF4 IN ACETONITRILE - SYNTHESIS AND STRUCTURE OF [MO2(MU-F)(NCCH3)8O2][BF4]3 Academic Article uri icon

abstract

  • Reaction of MoCl3(THF)3 with 3 equiv of AgBF4 in refluxing acetonitrile produces the unusual solvated MoIV-oxo complex [Mo2(-F)(NCCH3)8O2[BF4]3 (1) as a result of oxidation by silver(I), as well as abstraction of both a fluoride ion from [BF4]- and an oxygen atom from THF or adventitious water. Compound 1 has been investigated by 1H and 19F NMR, IR and UV-vis spectroscopy, electrochemistry and X-ray crystallography. Single crystal X-ray data collected at - 92 2C revealed that 1 is monoclinic, space group P2/n with a = 11.776(4), b = 12.293(7), c = 12.497(7) , = 100.90(4), V = 1776(1) 3 and Z = 2. Final refinement led to R = 0.038 and Rw = 0.059. The structural core of the molecule consists of the unusual group [OMoFMoO]3+ for which the angle MoFMo is 165.0. The pyramidal MoN4 units around each molybdenum(IV) centre are staggered with respect to one another, and as a result of the basal N plane being 0.27 from the molybdenum centre, the acetonitriles are canted towards the centre of the molecule forming a "cupped" central region around the bridging fluorine atom. This fluoride-bridged structure is unique among molybdenum(IV) dimers, and is one of only several documented examples in molybdenum chemistry. 1992.

published proceedings

  • POLYHEDRON

author list (cited authors)

  • MATONIC, J. H., CHEN, S. J., PENCE, L. E., & DUNBAR, K. R.

citation count

  • 13

complete list of authors

  • MATONIC, JH||CHEN, SJ||PENCE, LE||DUNBAR, KR

publication date

  • January 1992