Synthesis and characterization of novel phosphinoketone and phosphinoenolato rhenium(v) nitrido complexes. Crystal structure of ReNCl2{iPr2PCH2C(Ph)O}2

Couillens, Xavier; Gressier, Marie; Dartiguenave, Michèle; Fortin, Sébastien; Beauchamp, André L.

doi:10.1039/b201632j

Cited by 10 publications

(11 citation statements)

References 22 publications

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“…spectra were recorded on a Shimadzu UV-1601PC spectrophotometer and a Nicolet Magna IR series II spectrometer respectively. 1 …”

Section: Physical Measurementsmentioning

confidence: 97%

“…The electroneutral azoheterocycles used in the present work were 2-(chlorophenylazo)pyridine (L), (1). The reaction of Re(CO) 5 Cl with a slight excess of L proceeded smoothly according to Equation (1) in boiling benzene, furnishing a blue crystalline…”

Section: Synthetic Strategymentioning

confidence: 99%

“…In recent years the chemistry of rhenium has moved toward new applications in therapeutic nuclear medicine and new complexes have been developed for the selective delivery of cytotoxic radionuclides 186 Re and 188 Re to tumors [1]. We also note that, in particular, the chemistry of tricarbonylrhenium(I) is of abiding interest in the context of bioconjugate synthesis [2], anion radical formation [3], potential photophysical [4] and radiopharmaceutical [2,5] properties.…”

Section: Introductionmentioning

confidence: 98%

“…The richness of this reaction chemistry prompted us to explore the reactivity of pentacarbonyl (chloro) rhenium(I) chelates with the 2-(chlorophenylazo)pyridine (1) ligand leading to the formation of tricarbonylchlororhenium(I) chelates. The synthesis, structure and weak interactions in the solid state of this complex have been monitored.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and structure of the 2-(chlorophenylazo)pyridine chelated tricarbonylrhenium(I) complex and its anion radical derivatives via electrochemical reduction

Sengupta

Panda

2005

Transition Met Chem

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Reacting Re(CO) 5 Cl with the azopyridine ligand (1) (L) in boiling benzene afford the complex Re(CO) 3 Cl(L), (2) in excellent yield [L=2-(p-Cl-C 6 H 4 NN)C 5 H 4 N]. The chelation of the azopyridine ligand accompanied by displacement of the two carbon monoxide ligands furnish a five-membered chelate ring. Structure determination of complex (2) has revealed a distorted octahedral ReC 3 N 2 Cl coordination sphere. The Re-N(pyridine) and, Re-N(azo) distances are 2.158(3) and 2.153(6) Å respectively, and the N-N length [1.273(4) Å ], implicate relatively weak Re-azo(p*) back-bonding. The Re(CO) 3 Cl(L) lattice consists of C-HÁ Á ÁCl hydrogen bonding and ClÁ Á ÁO non-bonded interactions constituting a supramolecular network. Extended Hu¨ckel calculations reveal that the LUMO of Re(CO) 3 Cl(L) is Ca. 57% azo in character. One-electron quasireversible electrochemical reduction of the complex occurs near )0.3

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“…spectra were recorded on a Shimadzu UV-1601PC spectrophotometer and a Nicolet Magna IR series II spectrometer respectively. 1 …”

Section: Physical Measurementsmentioning

confidence: 97%

Section: Synthetic Strategymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and structure of the 2-(chlorophenylazo)pyridine chelated tricarbonylrhenium(I) complex and its anion radical derivatives via electrochemical reduction

Sengupta

Panda

2005

Transition Met Chem

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“…In recent years the chemistry of rhenium has moved toward new applications in the therapeutic nuclear medicine and new complexes have been developed for the selective delivery of cytotoxic radionuclides 186 Re and 188 Re to tumors 1 . Formation of oxido moieties constitute a dominant feature in the higher oxidation states of rhenium 2 .…”

Section: Introductionmentioning

confidence: 99%

Oxidorhenium(V) and Imidorhenium(V) Complexes of Pyridylpyridazine:Oxygen Atom Transfer, Oxidation and Substitution Involving Oxido, Phosphine Oxide and Phosphine Coordination

2015

Chem Sci Trans

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Unusual Structure, Fluxionality, and Reaction Mechanism of Carbonyl Hydrosilylation by Silyl Hydride Complex [(ArN)Mo(H)(SiH₂Ph)(PMe₃)₃]

Khalimon

Ignatov

Охапкин

et al. 2013

Chemistry A European J

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The reactions of bis(borohydride) complexes [(RN=)Mo(BH4)2(PMe3)2] (4: R = 2,6-Me2C6H3; 5: R = 2,6-iPr2C6H3) with hydrosilanes afford new silyl hydride derivatives [(RN=)Mo(H)(SiR'3)(PMe3)3] (3: R = Ar, R'3 = H2Ph; 8: R = Ar', R'3 = H2Ph; 9: R = Ar, R'3 = (OEt)3; 10: R = Ar, R'3 = HMePh). These compounds can also be conveniently prepared by reacting [(RN=)Mo(H)(Cl)(PMe3)3] with one equivalent of LiBH4 in the presence of a silane. Complex 3 undergoes intramolecular and intermolecular phosphine exchange, as well as exchange between the silyl ligand and the free silane. Kinetic and DFT studies show that the intermolecular phosphine exchange occurs through the predissociation of a PMe3 group, which, surprisingly, is facilitated by the silane. The intramolecular exchange proceeds through a new non-Bailar-twist pathway. The silyl/silane exchange proceeds through an unusual Mo(VI) intermediate, [(ArN=)Mo(H)2(SiH2Ph)2(PMe3)2] (19). Complex 3 was found to be the catalyst of a variety of hydrosilylation reactions of carbonyl compounds (aldehydes and ketones) and nitriles, as well as of silane alcoholysis. Stoichiometric mechanistic studies of the hydrosilylation of acetone, supported by DFT calculations, suggest the operation of an unexpected mechanism, in that the silyl ligand of compound 3 plays an unusual role as a spectator ligand. The addition of acetone to compound 3 leads to the formation of [trans-(ArN)Mo(OiPr)(SiH2Ph)(PMe3)2] (18). This latter species does not undergo the elimination of a Si-O group (which corresponds to the conventional Ojima's mechanism of hydrosilylation). Rather, complex 18 undergoes unusual reversible β-CH activation of the isopropoxy ligand. In the hydrosilylation of benzaldehyde, the reaction proceeds through the formation of a new intermediate bis(benzaldehyde) adduct, [(ArN=)Mo(η(2)-PhC(O)H)2(PMe3)], which reacts further with hydrosilane through a η(1)-silane complex, as studied by DFT calculations.

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Synthesis and characterization of novel phosphinoketone and phosphinoenolato rhenium(v) nitrido complexes. Crystal structure of ReNCl2{iPr2PCH2C(Ph)O}2

Cited by 10 publications

References 22 publications

Synthesis and structure of the 2-(chlorophenylazo)pyridine chelated tricarbonylrhenium(I) complex and its anion radical derivatives via electrochemical reduction

Synthesis and structure of the 2-(chlorophenylazo)pyridine chelated tricarbonylrhenium(I) complex and its anion radical derivatives via electrochemical reduction

Oxidorhenium(V) and Imidorhenium(V) Complexes of Pyridylpyridazine:Oxygen Atom Transfer, Oxidation and Substitution Involving Oxido, Phosphine Oxide and Phosphine Coordination

Unusual Structure, Fluxionality, and Reaction Mechanism of Carbonyl Hydrosilylation by Silyl Hydride Complex [(ArN)Mo(H)(SiH₂Ph)(PMe₃)₃]

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Synthesis and characterization of novel phosphinoketone and phosphinoenolato rhenium(v) nitrido complexes. Crystal structure of ReNCl2{iPr2PCH2C(Ph)O}2

Cited by 10 publications

References 22 publications

Synthesis and structure of the 2-(chlorophenylazo)pyridine chelated tricarbonylrhenium(I) complex and its anion radical derivatives via electrochemical reduction

Synthesis and structure of the 2-(chlorophenylazo)pyridine chelated tricarbonylrhenium(I) complex and its anion radical derivatives via electrochemical reduction

Oxidorhenium(V) and Imidorhenium(V) Complexes of Pyridylpyridazine:Oxygen Atom Transfer, Oxidation and Substitution Involving Oxido, Phosphine Oxide and Phosphine Coordination

Unusual Structure, Fluxionality, and Reaction Mechanism of Carbonyl Hydrosilylation by Silyl Hydride Complex [(ArN)Mo(H)(SiH2Ph)(PMe3)3]

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Unusual Structure, Fluxionality, and Reaction Mechanism of Carbonyl Hydrosilylation by Silyl Hydride Complex [(ArN)Mo(H)(SiH₂Ph)(PMe₃)₃]