An unusual complex derived from MoCl3(THF)3 and AgBF4 in acetonitrile: Synthesis and structure of [MO2(μ-F)(NCCH3)8O2][BF4]3
1992; Elsevier BV; Volume: 11; Issue: 5 Linguagem: Inglês
10.1016/s0277-5387(00)83301-x
ISSN1873-3719
AutoresJohn H. Matonic, Sue-Jane Chen, Laura E. Pence, Kim R. Dunbar,
Tópico(s)Inorganic Fluorides and Related Compounds
ResumoReaction of MoCl3(THF)3 with 3 equiv of AgBF4 in refluxing acetonitrile produces the unusual solvated MoIV-oxo complex [Mo2(μ-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 ± 2°C revealed that 1 is monoclinic, space group P2/n with a = 11.776(4), b = 12.293(7), c = 12.497(7) Å, β = 100.90(4)°, V = 1776(1) Å3 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 Å 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.
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