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

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.