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Issue 3, 2001
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Synthesis and characterisation of {Mo(η-L)(CO)3}+ (η-L = C5H5 or C5Me5) fragments ligated with [CB11H12] and derivatives. Isolation and structural characterisation of an intermediate in a silver saltmetathesis reaction

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Abstract

The synthesis of {Mo(η-L)(CO)3}+ (η-L = C5H5 or C5Me5) fragments, ligated to the mono-anionic, weakly co-ordinating, carboranes [closo-1-CB11H12] and [closo-CB11Br6H6], has been investigated. Treatment of [MoCp(CO)3X] (X = Cl or I) with Ag[CB11H12] eventually affords the zwitterionic complex [MoCp(CO)3(x-μ-H-1-CB11H12)] (x = 12 or 7), via an intermediate dimeric species [MoCp(CO)3X·Ag(CB11H12)]2. For X = I this intermediate has been characterised by 1H, 11B NMR spectroscopy and X-ray crystallography and represents the first structurally characterised intermediate in a silver salt metathesis reaction. When the less nucleophilic carborane [CB11Br6H6] (as its silver salt) is used metathesis is halted at the intermediate stage, affording the complex [MoCp(CO)3I·Ag(CB11Br6H6)]2. Silver salt metathesis does not proceed using the sterically more demanding [Mo(Cp*)(CO)3I], with only intractable products isolated. The carborane anion can be introduced into the co-ordination sphere of this complex by reaction of [H(OEt2)x][CB11H12] with [Mo(Cp*)(CO)3Me] affording [Mo(Cp*)(CO)3(x-μ-H-1-CB11H12)] (x = 12 or 7). All new compounds have been characterised by multinuclear NMR spectroscopy and X-ray crystallography.

Graphical abstract: Synthesis and characterisation of {Mo(η-L)(CO)3}+ (η-L = C5H5 or C5Me5) fragments ligated with [CB11H12]− and derivatives. Isolation and structural characterisation of an intermediate in a silver salt metathesis reaction

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Article information


Submitted
12 Oct 2000
Accepted
22 Nov 2000
First published
11 Jan 2001

J. Chem. Soc., Dalton Trans., 2001, 277-283
Article type
Paper

Synthesis and characterisation of {Mo(η-L)(CO)3}+ (η-L = C5H5 or C5Me5) fragments ligated with [CB11H12] and derivatives. Isolation and structural characterisation of an intermediate in a silver salt metathesis reaction

N. J. Patmore, M. F. Mahon, J. W. Steed and A. S. Weller, J. Chem. Soc., Dalton Trans., 2001, 277
DOI: 10.1039/B008222H

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