Ruthenium(II) complexes of 3,4-dimethylphosphacymantrene

Brunet, Lionel; Mercier, François; Ricard, Louis; Mathey, François

doi:10.1016/s0277-5387(00)83099-5

Cited by 6 publications

(2 citation statements)

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“…210 The reaction of 8 with 4 equiv of 3,4-dimethylphosphacymantrene (dmpcym, phosphacymantrene ) η 5 -phosphacyclopentadienyl-manganesetricarbonyl, Chart 16) in THF at 40°C produced cisRuCl 2 (dmpcym) 4 . 211 Treatment of 8 with methoxydiphenylphosphine (Ph 2 POMe) in refluxing methanol yielded the five-coordinate phosphinite complex RuCl 2 (Ph 2 POMe) 3 , which in the solid state has a triply chloro-bridged dimeric structure, [{Ru(Ph 2 -POMe) 3 } 2 (µ-Cl) 3 ]Cl. 212,213 The reaction of 8 with 3 equiv of triphenylphosphine monosulfonate (tppms) in refluxing toluene apparently afforded the watersoluble cis-RuCl 2 (dmso-S)(tppms) 3 complex.…”

Section: Monodentate P As and Sb Ligandsmentioning

confidence: 99%

“…15 The group of Dixneuf reported that the reaction of 8 with 1 equiv of the bulky tricyclohexylphosphine (Pcy 3 ) in dichloromethane at ambient temperature gives the five-coordinate complex RuCl 2 (dmso-S) 2 (Pcy 3 ), while a six-coordinate RuCl 2 (dmso-S) 2 (Pcy 3 ) 2 complex of undetermined geometry was isolated when 2 equiv of Pcy 3 were used; 209 210 The reaction of 8 with 4 equiv of 3,4dimethylphosphacymantrene (dmpcym, phosphacymantrene ) η 5 -phosphacyclopentadienyl-manganesetricarbonyl, Chart 16) in THF at 40 °C produced cis-RuCl 2 (dmpcym) 4 . 211 Treatment of 8 with methoxydiphenylphosphine (Ph 2 POMe) in refluxing methanol yielded the five-coordinate phosphinite complex RuCl 2 (Ph 2 POMe) 3 , which in the solid state has a triply chloro-bridged dimeric structure, [{Ru(Ph 2 -POMe) 3 } 2 (µ-Cl) 3 ]Cl. 212,213 The reaction of 8 with 3 equiv of triphenylphosphine monosulfonate (tppms) in refluxing toluene apparently afforded the watersoluble cis-RuCl 2 (dmso-S)(tppms) 3 complex.…”

Section: Monodentate P As and Sb Ligandsmentioning

confidence: 99%

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Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

2004

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Section: Monodentate P As and Sb Ligandsmentioning

confidence: 99%

Section: Monodentate P As and Sb Ligandsmentioning

confidence: 99%

Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

2004

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Redox‐Induced Coordination Isomerization of a Phosphoniobenzophospholide

Gudat

Lewall

Nieger

et al. 2003

Chemistry A European J

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1-Triphenylphosphoniobenzo[c]phospholide 1 reacts with [M(CO)(5)Br] (M = Mn, Re) and [Mn(CO)(3)(naphthalene)][BF(4)] to give complexes cis-[M(CO)(4)(1)Br] (5 a,b) and [Mn(CO)(3)(1)][BF(4)] (6 a[BF(4)]), respectively, featuring eta(1)(P)- and eta(5)(pi)-coordination of the phosphole ring. The corresponding reactions with [M(2)(CO)(10)] proceed with conservation of the metal-metal bond and yield, depending on the reaction temperature, dinuclear complexes [M(2)(CO)(8)(1)] (M=Mn, 7 a) or [M(2)(CO)(6)(1)(2)] (M=Mn, Re, 8 a,b) with mu(2)-bridging eta(1)(P):eta(2)(Pdbond;C) coordination of the phosphole moiety. All complexes formed were characterized by spectroscopic data; 5 b, 6 a[BF(4)], and 8 a,b were characterized by X-ray diffraction studies as well. The structural and (31)P NMR data of the dinuclear manganese complex 8 a suggest that the interaction between the metal atoms and the eta(2)-bound Pdbond;C double bond moieties is dominated by the L-->M charge-transfer contribution; this hints at a very low back-donation ability of the central M(2)(CO)(6) fragment. Investigation of the reactions of the Mn complexes 6 a and 8 a with Mg or ferrocenium hexafluorophosphate ([Fc][PF(6)]), respectively, revealed that the chemically reversible mutual interconversion between both species was feasible. Likewise, oxidation of the rhenium complex 8 b with [Fc][PF(6)] gave spectroscopic evidence for the formation of a Re analogue of 6 a. Electrochemical studies suggested that the oxidation 8 a-->2 6 a involves two consecutive single-electron-transfer steps, the first of which is electrochemically reversible and produces a metastable radical cation that is detectable by ESR spectroscopy. The mutual interconversion between 6 a and 8 a represents the first case of a reversible coordination isomerization of a phosphaarene that is triggered by a redox process and might stimulate further studies directed at the use of dinuclear phosphaarene complexes in redox-catalysis.

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