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molybdocene dichloride : ウィキペディア英語版
molybdocene dichloride

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Molybdocene dichloride is the organomolybdenum compound with the formula (η5-C5H5)2MoCl2 and IUPAC name dichlorobis(η5-cyclopentadienyl)molybdenum(IV), and is commonly abbreviated as Cp2MoCl2. It is a brownish-green air- and moisture-sensitive powder. In the research laboratory, it is used to prepare many derivatives.
==Preparation and structure==
The compound was first reported in 1964 by Malcolm Green and his student Cooper.〔R. L. Cooper and M. L. H. Green, ''Z. Naturforsch., B: Anorg. Chem. Org. Chem.'' 1964, volume 19, pp. 652. R. L. Cooper and M. L. H. Green, ''J. Chem. Soc. (A)'', 1967, p. 1155.〕 It is prepared from molybdocene dihydride, which in turn is prepared by a famously complex reaction involving molybdenum pentachloride, sodium cyclopentadienide, and sodium borohydride. The dihydride converts to the dichloride upon treatment with chloroform:
:(C5H5)2MoH2 + 2 CHCl3 → (C5H5)2MoCl2 + 2 CH2Cl2
The compound adopts a "clamshell" structure where the Cp rings are not parallel, the average Cp(centroid)-M-Cp angle being 130.6°. The two chloride ligands are cis, the Cl-Mo-Cl angle of 82° being narrower than in niobocene dichloride (85.6°), which in turn is less than in zirconacene dichloride (92.1°). This trend helped to establish the orientation of the HOMO in this class of complex.〔K. Prout, T. S. Cameron, R. A. Forder, and in parts S. R. Critchley, B. Denton and G. V. Rees "The crystal and molecular structures of bent bis-π-cyclopentadienyl-metal complexes: (a) bis-π-cyclopentadienyldibromorhenium(V) tetrafluoroborate, (b) bis-π-cyclopentadienyldichloromolybdenum(IV), (c) bis-π-cyclopentadienylhydroxomethylaminomolybdenum(IV) hexafluorophosphate, (d) bis-π-cyclopentadienylethylchloromolybdenum(IV), (e) bis-π-cyclopentadienyldichloroniobium(IV), (f) bis-π-cyclopentadienyldichloromolybdenum(V) tetrafluoroborate, (g) μ-oxo-bis() tetrafluoroborate, (h) bis-π-cyclopentadienyldichlorozirconium" ''Acta Cryst.'' 1974, volume B30, pp. 2290–2304. 〕

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