Cyclometallation of bis(diphenylphos-phino)methane ligands on a binuclear ruthenium(0) carbonyl complex

Mirza, Hameed A.; Vittal, Jagadese J.; Puddephatt, Richard J.

doi:10.1139/v95-113

Cited by 7 publications

(2 citation statements)

References 12 publications

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“…Evidence for spontaneous cycloruthenation occurring upon C–P bond cleavage has been reported by Bruce for the thermolysis of Ru 3 (μ‐dppm)(CO) 10 , (dppm = diphenylphosphanylmethane) which affords a new Ru 3 cluster, 69 , containing a μ‐hydrido ligand and a large fragment of the rearranged bis(diphenylphosphanyl)methane ligand (Figure 7). 124 The reader should also refer to other similar findings by Puddephatt et al with dinuclear carbonylruthenium complexes of dppm 125…”

Section: Cycloruthenationmentioning

confidence: 78%

Cycloruthenated Compounds – Synthesis and Applications

et al. 2009

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The syntheses of cycloruthenated compounds by several methods, and especially by the C-H activation pathway, have been reviewed. Many ruthenium-containing starting materials lead to these interesting organometallic compounds, which have found various applications in different fields of chemistry. Their reactivity highlights both the variety of reactions that were found to occur at the Ru-C bonds as well as the inertness of the organometallic moiety when these species are exposed to strongly oxidizing molecules or to reactive halogenation reagents. Their use as catalyst precursors showed them to be particularly efficient for hydrogenation reactions, either by H 2 or by hydride transfer.

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Section: Cycloruthenationmentioning

confidence: 78%

Cycloruthenated Compounds – Synthesis and Applications

et al. 2009

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“…As this unusual assisted reaction and mechanism should not be restricted to this N,P ligand, we undertook the study of a similar reaction with the much used diphenylphosphine ligand (dppm) . Some examples of P−C and C−H bond activations of metal−metal bonds in the reactions of dppm with ruthenium and osmium clusters have been described, , and cyclometalation of a phenyl ring of dppm taking place at the same metal to which the phosphorus is bound has been observed in a heterodinuclear complex . Supporting this idea, a binuclear sp 2 -C−H bond activation across the two metals also occurs in the reaction of dppm with [{Ir(R-Cl)(cod) 2 ] in a 1:1 molar ratio in dichloromethane.…”

Section: Resultsmentioning

confidence: 97%

Reversible C−H Bond Activation of a Bifunctional Phosphine Bridging Ligand across Two Unbonded Metal Centers

et al. 2000

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Reaction of [{Ir(µ-Cl)(cod)} 2 ] with the short-bite bifunctional N,P-donor ligand (1-benzyl-2-imidazolyl)diphenylphosphine (Ph 2 PBzIm) gives the yellow complex [IrCl(Ph 2 PBzIm)(cod)] (2). A further addition of [{Ir(µ-Cl)(cod)} 2 ] to 2 results in the reversible metalation of a phenyl ring across two unbonded iridium centers to give orange crystals of [IrCl(cod){µ-PPh(C 6 H 4 )-BzIm}IrHCl(cod)] (1). Complex 1 is in equilibrium with the mononuclear complex [IrCl(Ph 2 -PBzIm)(cod)] and the active species undergoing the sp 2 -C-H activation, [{IrCl(cod)} 2 (µ-Ph 2 PBzIm)], in solution. Abstraction of one chloride ligand from 1 with AgBF 4 produces the deinsertion of the C-H bond yielding the cationic complex [{Ir(cod)} 2 (µ-Ph 2 PBzIm)(µ-Cl)]-BF 4 , which regenerates 1 upon addition of a chloride-soluble salt. The cationic complex [{Ir-(cod)} 2 (µ-Ph 2 PBzIm)(µ-Cl)]BF 4 is inactive for the above-mentioned sp 2 -C-H bond activation and can be prepared alternatively from the reaction of 2 with [Ir(cod)(CH 3 CN) 2 ]BF 4 . A related binuclear sp 2 -C-H bond activation across two unbonded metals also occurs in the reaction of dppm with [{Ir(µ-Cl)(cod)} 2 ] in a 1:1 molar ratio. This reaction leads to a mixture in equilibrium of [{IrCl(cod)} 2 (µ-dppm)] and the hydride complex [IrCl(cod){µ-PPh(C 6 H 4 )CH 2 -PPh 2 )}IrHCl(cod)] in a 1.5:1 molar ratio, respectively, in dichloromethane at 20 °C. The structure of the mixed-valence complex 1 was solved by X-ray diffraction studies. Scheme 1 Scheme 2

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Dinuclear Ru/Os Compounds with Metal–Metal Bonds

Wilton‐Ely

2007

Comprehensive Organometallic Chemistry III

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Cyclometallation of bis(diphenylphos-phino)methane ligands on a binuclear ruthenium(0) carbonyl complex

Abstract: Abstract:The first example of simple orthometallation of a bis(dipheny1phosphino)methane ligand at a binuclear centre is reported. Both dppm ligands of the binuclear ruthenium (0)

Cited by 7 publications

References 12 publications

Cycloruthenated Compounds – Synthesis and Applications

Cycloruthenated Compounds – Synthesis and Applications

Reversible C−H Bond Activation of a Bifunctional Phosphine Bridging Ligand across Two Unbonded Metal Centers

Dinuclear Ru/Os Compounds with Metal–Metal Bonds

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