Activation of All Bonds of a Methyl Group Attached to an Organic Fragment

Cabeza, Javier A.; Silva, Iván da; Rı́o, Ignacio del; Martínez‐Méndez, Lorena; Miguel, Daniel

doi:10.1002/ange.200454066

Cited by 5 publications

(1 citation statement)

References 47 publications

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“…[38][39][40] Osmium cluster-NHC derivatives have only recently been reported [41][42][43] as having ruthenium derivatives. 41,[44][45][46][47] The lack of research in this area is surprising since the role of phosphines in cluster chemistry has been well documented and thoroughly explored. A key feature of small clusters containing transition metals is the ability of the metal sites to react in concert.…”

Section: Introductionmentioning

confidence: 99%

NHC Complexes of Osmium Clusters: A Structural and Reactivity Study

et al. 2008

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A carbene transfer agent, 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene-silver(I)chloride ([IMes]-AgCl), was treated with various osmium clusters. Reaction of ([IMes]AgCl) with [Os 3 (µ-H) 2 (CO) 10 ] gave [Os 3 (µ-H)(µ-Cl)(CO) 9 (IMes)] (1), an osmium N-heterocyclic carbene complex. The reaction of ([IMes]AgCl) with the cluster [Os 3 (CO) 10 (CH 3 CN) 2 ] yielded two products, [Os 3 (µ-Cl)(CO) 10 (µ-Ag(IMes)] (2) and [(IMes-H)][Os 3 (µ-Cl)(CO) 10 ](µ 4 -Ag)[Os 3 (µ-Cl)(CO) 10 ] (3). Compound (2) is a heterobimetallic carbene complex resulting from the complete incorporation of ([IMes]AgCl). Transmetalation using [(IMes)AgCl] and the cluster [Os 4 (µ-H) 4 (CO) 12 ] in the presence of trimethylamine-N-oxide resulted in the formation of [Os 4 (µ-H) 4 (CO) 11 (n • IMes)] (4), where (n denotes normal carbene bonding, i.e., through C 2 ). [Os 4 (µ-H) 4 (CO) 10 (IMes) 2 ] (5) was formed using the activated cluster [Os 4 (µ-H) 4 (CO) 10 (CH 3 CN) 2 ] and [(IMes)AgCl]. Compound (5) was found to be sensitive to silica gel column chromatography in the presence of dichloromethane decomposing to [Os 4 (µ-H) 3 (µ-Cl)(CO) 11 (IMes)] ( 6), which possessed a butterfly metal skeleton. The ruthenium analogue of ( 4), [Ru 4 (µ-H) 4 (CO) 11 (IMes)] ( 7), was prepared and identified spectroscopically but was found to be thermally unstable. Thermolysis of (4) in benzene yielded four products. The abnormal carbene complex [Os 4 (µ-H) 4 (CO) 11 (a • IMes)] (10) (a denotes abnormal carbene bonding through C 3 or C 4 ), an isomer of (4), and {Os 4 (µ-H 11), an unusual complex resulting from the activation of benzene and activation of three C-H bonds on IMes, were isolated in modest yields. Two higher-nuclearity clusters, {Os 5 (µ 5 -C)(CO) 14 [η-C-η-NC 2 H 2 (Mes)]} ( 8) and [Os 6 (µ-H) 4 (µ 5 -C)(CO) 15 (IMes)] ( 9), both of which contain carbide ligands, were also isolated. {Os 4 (µ-H)(CO) 10 [(η-C)N(Mes)C 2 H 2 NC 6 H 2 (CH 3 ) 2 (η 2 -C)(η-C)CHC(CH 3 )-C 2 H 2 (η 2 -C)]} (12), an analogue of (10), resulted from the thermolysis of (4) in toluene indicates that the reaction is potentially general and exhibits some regioselectivity. Crystal structure determinations were completed on all 11 osmium cluster complexes.

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Section: Introductionmentioning

confidence: 99%

NHC Complexes of Osmium Clusters: A Structural and Reactivity Study

et al. 2008

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From an N‐Methyl N‐Heterocyclic Carbene to Carbyne and Carbide Ligands via Multiple CH and CN Bond Activations

Cabeza¹,

Rı́o²,

Miguel³

et al. 2008

Angewandte Chemie

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From an N‐Methyl N‐Heterocyclic Carbene to Carbyne and Carbide Ligands via Multiple CH and CN Bond Activations

et al. 2008

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Multiple choices: The carbyne C atom of 1 and the carbide of 2 arise from an N‐methyl group of 1,3‐dimethylimidazol‐2‐ylidene. The synthesis of complex 1, which involves activation of the three CH bonds of an N‐methyl group, and that of complex 2, which requires additional activation of the CN bond, provide new examples of metal‐mediated degradation of N‐heterocyclic carbenes.

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Activation of All Bonds of a Methyl Group Attached to an Organic Fragment

Cited by 5 publications

References 47 publications

NHC Complexes of Osmium Clusters: A Structural and Reactivity Study

NHC Complexes of Osmium Clusters: A Structural and Reactivity Study

From an N‐Methyl N‐Heterocyclic Carbene to Carbyne and Carbide Ligands via Multiple CH and CN Bond Activations

From an N‐Methyl N‐Heterocyclic Carbene to Carbyne and Carbide Ligands via Multiple CH and CN Bond Activations

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