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

Nathan J. Patmore, Mary F. Mahon, Jonathan W. Steed, Andrew S. Weiler

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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-l-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.

LanguageEnglish
Pages277-283
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number3
Early online date11 Jan 2001
DOIs
Publication statusPublished - 12 Jan 2001
Externally publishedYes

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Carbon Monoxide
Silver
Salts
Derivatives
X ray crystallography
Nuclear magnetic resonance spectroscopy
Anions

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title = "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",
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-l-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.",
author = "Patmore, {Nathan J.} and Mahon, {Mary F.} and Steed, {Jonathan W.} and Weiler, {Andrew S.}",
year = "2001",
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T1 - 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

AU - Patmore, Nathan J.

AU - Mahon, Mary F.

AU - Steed, Jonathan W.

AU - Weiler, Andrew S.

PY - 2001/1/12

Y1 - 2001/1/12

N2 - The synthesis of {Mo(η-L)(CO)3}+ (η-L = C5H5 or C5Me5) fragments, ligated to the mono-anionic, weakly co-ordinating, carboranes [closo-l-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.

AB - The synthesis of {Mo(η-L)(CO)3}+ (η-L = C5H5 or C5Me5) fragments, ligated to the mono-anionic, weakly co-ordinating, carboranes [closo-l-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.

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T2 - Journal of the Chemical Society. Dalton Transactions

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