Dealkylation of methyl isocyanide in platinum complexes of this ligand

Treichel, P. M.; Hess, R. W.

doi:10.1039/c29700001626

Cited by 13 publications

(5 citation statements)

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“…The elimination of the R group from a coordinated alkylisocyanide has been reported before. − In most cases the isocyanide involved is CNBu t , , as in the present example, and normally the elimination is thermally induced; for example, heating [Ru(CNBu t ) 6 ][PF 6 ] 2 under reflux in n -propanol for 12 h produces [Ru(CNBu t ) 5 (CN)][PF 6 ]. However, in none of these prior reports has elimination been triggered by coordination of another ligand to the metal, and in none has the resulting cyano group not been directly coordinated to the metal.…”

Section: Discussionsupporting

confidence: 68%

Ligand-Induced and Reductively Induced Alkyne−Isocyanide Coupling Reactions of [Mo(CNBu^t)₃(PhC⋮CPh)(η⁵-C₅Me₅)][BF₄]

et al. 2002

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The complex [Mo(CO)(PhC⋮CPh)2(η5-C5Me5)][BF4] reacts with 3 equiv of CNBut to yield the mixed alkyne−isocyanide complex [Mo(CNBut)3(PhC⋮CPh)(η5-C5Me5)][BF4], 1. Reaction of 1 with a fourth equivalent of CNBut generates [Mo{C(NHBut)C(Ph)C(Ph)CN}(CNBut)2(η5-C5Me5)][BF4], 2, containing an η3-vinylcarbene ligand formed from the coupling of two of the coordinated isocyanide ligands with the diphenylacetylene, with concomitant protonation of one of these isocyanide fragments and dealkylation of the other. Complex 2 may be deprotonated to give [Mo{C(NBut)C(Ph)C(Ph)CN}(CNBut)2(η5-C5Me5)], 3. Protonation of 1 with HBF4·Et2O generates [Mo{C(Ph)C(Ph)CNHBut}(CNBut)2(η5-C5Me5)][BF4]2, 4, by inducing the coupling of a protonated isocyanide ligand with diphenylacetylene, and 4 reacts with CNBut to give 2. A similar reaction of 4 with P(OMe)3 generates [Mo{C(NHBut)C(Ph)C(Ph)CN}(CNBut){P(OMe)3}(η5-C5Me5)][BF4], 5, involving the same coupling and elimination pattern. The diphenylacetylene and CNBut ligands of 1 may also be reductively coupled. Thus, treatment of 1 with sodium−mercury amalgam and subsequent protonation with HBF4·Et2O gives the metallacyclopentatriene-like [Mo{C(NHBut)C(Ph)C(Ph)C(NHBut)}(CNBut)(η5-C5Me5)][BF4], 6, or [Mo{C(NHBut)C(Ph)C(Ph)CH−NHBut}(CNBut)(η5-C5Me5)][BF4], 7, depending upon the solvent. Complex 7 contains an N-protonated η4-monoazadiene ligand with a pendant carbene functionality that is also coordinated to the metal. The crystal structures of 1, 2, 3, 6, and 7 have been determined.

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Section: Discussionsupporting

confidence: 68%

Ligand-Induced and Reductively Induced Alkyne−Isocyanide Coupling Reactions of [Mo(CNBu^t)₃(PhC⋮CPh)(η⁵-C₅Me₅)][BF₄]

et al. 2002

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“…Before the year 2000, the dealkylation of isocyanides was reported for Sm, Ti, Zr, V, Mo, − Tc, Re, Ru, − Os, Co, Rh, Pt, − and Cu metal centers.…”

Section: Cleavage Of the Cn–r Single Bond At Metal Centersmentioning

confidence: 99%

Metal-Mediated and Metal-Catalyzed Reactions of Isocyanides

et al. 2015

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“…No attempt was made to determine the fate of the leaving t -Bu group. Indeed, cleavage of the N−C single bond of an isocyanide has previously been accomplished either by straightforward thermal decomposition of a cationic transition metal compound , or by thermolysis of ML n complexes in the presence of excess isocyanide under both harsh 16 and mild 12,17 conditions. Although, the fate of the tert -butyl group has not been systematically determined in these previous works, the formation of either tert -butyl alcohol or isobutylene has been proposed.…”

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confidence: 99%

Unexpected Coupling of Cp and Two RNC Ligands at a {Mo₂(μ-SMe)₃} Nucleus

et al. 2003

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Reaction of the bis-isonitrile complex [Mo2Cp2(μ-SMe)3(t-BuNC)2](BF4) (1) with n-BuLi (in hexane) produced the dealkylated derivative [Mo2Cp2(μ-SMe)3(t-BuNC)(CN)] (2) in quantitative yield. However, upon treatment with either NaOH (suspension) or (Me4N)OH (in MeOH), 1 was converted into a mixture of 2 and the μ-alkylidyne species [Mo2Cp(μ-SMe)3{μ-(η5-C5H4)(t-BuN)CN(t-Bu)C}] (3), in which a deprotonated Cp and both isonitrile ligands of 1 are now linked by new carbon−carbon and carbon−nitrogen bonds.

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Dealkylation of methyl isocyanide in platinum complexes of this ligand

Cited by 13 publications

References 0 publications

Ligand-Induced and Reductively Induced Alkyne−Isocyanide Coupling Reactions of [Mo(CNBu^t)₃(PhC⋮CPh)(η⁵-C₅Me₅)][BF₄]

Ligand-Induced and Reductively Induced Alkyne−Isocyanide Coupling Reactions of [Mo(CNBu^t)₃(PhC⋮CPh)(η⁵-C₅Me₅)][BF₄]

Metal-Mediated and Metal-Catalyzed Reactions of Isocyanides

Unexpected Coupling of Cp and Two RNC Ligands at a {Mo₂(μ-SMe)₃} Nucleus

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Dealkylation of methyl isocyanide in platinum complexes of this ligand

Cited by 13 publications

References 0 publications

Ligand-Induced and Reductively Induced Alkyne−Isocyanide Coupling Reactions of [Mo(CNBut)3(PhC⋮CPh)(η5-C5Me5)][BF4]

Ligand-Induced and Reductively Induced Alkyne−Isocyanide Coupling Reactions of [Mo(CNBut)3(PhC⋮CPh)(η5-C5Me5)][BF4]

Metal-Mediated and Metal-Catalyzed Reactions of Isocyanides

Unexpected Coupling of Cp and Two RNC Ligands at a {Mo2(μ-SMe)3} Nucleus

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Ligand-Induced and Reductively Induced Alkyne−Isocyanide Coupling Reactions of [Mo(CNBu^t)₃(PhC⋮CPh)(η⁵-C₅Me₅)][BF₄]

Ligand-Induced and Reductively Induced Alkyne−Isocyanide Coupling Reactions of [Mo(CNBu^t)₃(PhC⋮CPh)(η⁵-C₅Me₅)][BF₄]

Unexpected Coupling of Cp and Two RNC Ligands at a {Mo₂(μ-SMe)₃} Nucleus