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Issue 10, 1993
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Imido and oxo compounds of chromium-(V) and -(VI) and of molybdenum- and tungsten-(VI)

Hon-wah Lam,  Geoffrey Wilkinson,  Bilquis Hussain-Bates  and  Michael B. Hursthouse 

Abstract

The interaction of 1,1,1,3,3,3-hexamethyldisilazane and CrO2Cl2 gives the amido complex CrO2[N(SiMe3)2] whereas MoO2Cl2 gives the imido complex Mo(NSiMe3)2(OSiMe3)2 and WO2Cl2(dme)(dme = 1,2-dimethoxyethane) gives a red oil that reacts with pyridine (py) to give WCl(NSiMe3)(OSiMe3)3(py). Interaction of CrO2[N(SiMe3)2] with pyridine and 4-methylpyridine (L) leads to reduction to the chromium(V) species [CrO(NSiMe3)L]2(µ-OSiMe3)2. Interaction of CrO2Cl2 with 2,2,6,6-tetramethyl-piperidine gives the amido species CrO2Cl(NC9H18) while SiMe2(NHBut)2 gives Cr(NBut)2Cl2(NH2But). The crystal structures of the compounds [CrO(NSiMe3)(py)]2(µ-OSiMe3)2, CrO2Cl(NC9H18) and WCl(NSiMe3)(OSiMe3)3(py) have been determined. In the centrosymmetric dimeric complex the Cr atom is five-co-ordinate with a geometry intermediate between trigonal bipyramidal and square pyramidal. The crystals of CrO2Cl(NC9H18) contain two chemically equivalent tetrahedral molecules, while WCl(NSiMe3)(OSiMe3)(py) is octahedral with the pyridine ligand trans to the imido group.

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Article type: Paper
DOI: 10.1039/DT9930001477
Citation: J. Chem. Soc., Dalton Trans., 1993,0, 1477-1482
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    Imido and oxo compounds of chromium-(V) and -(VI) and of molybdenum- and tungsten-(VI)

    H. Lam, G. Wilkinson, B. Hussain-Bates and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1993, 0, 1477
    DOI: 10.1039/DT9930001477

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