Syntheses with η5-C5H5V(CO)3THF: Generation, and substitution reactions. First observation of 51V-117,119Sn coupling

Hoch, Martin; Rehder, Dieter

doi:10.1016/0022-328x(85)87284-3

Cited by 24 publications

(8 citation statements)

References 27 publications

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“…Of complexes of metal cyclopentadienyl carbonyls with diorganyl tellurides, compounds of Group V elements, vanadium 123,124 and niobium, 125 have been described. These complexes, having the composition CpM(CO) 3 TeR 2 115, are prepared by exposure of a solution of tetracarbonyl(cyclopentadienyl)-vanadium or -niobium and a large excess of a diorganyl telluride to UV or visible light.…”

Section: Rh(co)(teet2)2meicl+comentioning

confidence: 99%

Synthesis, reactions and structures of complexes of metal carbonyls and cyclopentadienyl carbonyls with organotellurium ligands

Sadekov¹,

Ураев²,

Garnovskii³

1999

Russ. Chem. Rev.

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Section: Rh(co)(teet2)2meicl+comentioning

confidence: 99%

Synthesis, reactions and structures of complexes of metal carbonyls and cyclopentadienyl carbonyls with organotellurium ligands

Sadekov¹,

Ураев²,

Garnovskii³

1999

Russ. Chem. Rev.

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“…26 It was therefore not surprising when we found that addition of excess TsOH to [CpV(CO) 3 H] − in MeCN resulted in vigorous effervescence and the formation of CpV(CO) 3 MeCN (observable by IR and 1 H NMR). 27 The series of reactions between [CpV(CO) and S2). This observation offers further evidence that the first electrochemical event is the oxidation of [CpV(CO 3 H] − ; we suggest that the event at −0.39 V involves CpV-(CO) 3 (MeCN).…”

Section: ■ Resultsmentioning

confidence: 99%

Thermodynamics of H⁺/H^•/H^–/e^– Transfer from [CpV(CO)₃H]⁻: Comparisons to the Isoelectronic CpCr(CO)₃H

et al. 2019

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Hydrogen atom (H•) donors generated from H2 facilitate the atom efficient reduction of small molecule substrates. However, generating H• donors with X–H bond dissociation free energies (BDFEs) below 52 kcal mol–1 is especially challenging because they thermodynamically favor the bimolecular evolution of H2. We have recently proposed that [CpV(CO)3H]− catalyzes the conversion of H2 into a proton, an electron, and a hydrogen atom in the presence of a sacrificial base. In order to understand the driving force for H• transfer, the free energies of H+/H•/H–/e– transfer from [CpV(CO)3H]− have been evaluated using solution phase techniques and state-of-the-art quantum chemical calculations. Thermochemical cycles have been constructed in order to anchor the computational values against experimental observations. This facilitates a quantitative comparison of the thermodynamic driving force for H+/H•/H–/e– transfer between isoelectronic anionic/neutral hydrides of the same row (the corresponding values are already available for CpCr(CO)3H). The overall charge greatly influences the thermodynamics of transferring H+, H–, and e– (i.e., [CpV(CO)3H]− is a much weaker acid, a stronger hydride donor, and a stronger reductant than CpCr(CO)3H); there is almost no change in the thermodynamics of H• transfer (V–H BDFE 54.7 kcal mol, Cr–H BDFE 57.0 kcal mol–1). In MeCN, the one electron oxidation of [CpV(CO)3H]− (−0.83 V vs Fc/Fc+) generates CpV(CO)3H, which spontaneously evolves H2. The resulting CpV(CO)3 is trapped as the solvent adduct CpV(CO)3(MeCN). Because H• transfer is now coupled to metal–solvent binding, the V–H bond is substantially weakened for CpV(CO)3H (V–H BDFE 36.1 kcal mol–1), amounting to a strategy for obtaining very reactive H atoms from H2.

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“…nCp V X 2 (PR 3 ) 2 + Μ -> Μ X" + »/ 2 n[Cp V X(PR 3 )] 2 + VinPR·, (22) The role of MXn is to force the reaction to the dimeric vanadium (II) complexes through complexation of the liberated phosphines since the presence of free phosphine in solution complicates the synthesis of the dimeric complexes participating in an equilibrium equation (23). The monomeric character of these complexes is indicated by the mass spectrum and magnetic properties /48/.…”

Section: Structural Data Of Monocyclopentadienyl Compounds Of Vanadiumentioning

confidence: 99%

“…The vanadium (III) dihalide complexes CpVX 2 (PR 3 ) 2 (X=Cl,R=Me,Et; X=Br,R=Et) can be reduced with Al or Zn in THF to give dimeric vanadium (II) complexes [CpVX(PR 3 )] 2 , 7, according to the general equation (22). Methylcyclopentadienyl compounds are accessible by the same method.…”

Section: Structural Data Of Monocyclopentadienyl Compounds Of Vanadiumentioning

confidence: 99%

Monocyclopentadienyl Compounds of Vanadium

Avilés¹,

Teixeira²

1992

Reviews in Inorganic Chemistry

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Syntheses with η5-C5H5V(CO)3THF: Generation, and substitution reactions. First observation of 51V-117,119Sn coupling

Cited by 24 publications

References 27 publications

Synthesis, reactions and structures of complexes of metal carbonyls and cyclopentadienyl carbonyls with organotellurium ligands

Synthesis, reactions and structures of complexes of metal carbonyls and cyclopentadienyl carbonyls with organotellurium ligands

Thermodynamics of H⁺/H^•/H^–/e^– Transfer from [CpV(CO)₃H]⁻: Comparisons to the Isoelectronic CpCr(CO)₃H

Monocyclopentadienyl Compounds of Vanadium

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Syntheses with η5-C5H5V(CO)3THF: Generation, and substitution reactions. First observation of 51V-117,119Sn coupling

Cited by 24 publications

References 27 publications

Synthesis, reactions and structures of complexes of metal carbonyls and cyclopentadienyl carbonyls with organotellurium ligands

Synthesis, reactions and structures of complexes of metal carbonyls and cyclopentadienyl carbonyls with organotellurium ligands

Thermodynamics of H+/H•/H–/e– Transfer from [CpV(CO)3H]−: Comparisons to the Isoelectronic CpCr(CO)3H

Monocyclopentadienyl Compounds of Vanadium

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Product

Resources

About

Thermodynamics of H⁺/H^•/H^–/e^– Transfer from [CpV(CO)₃H]⁻: Comparisons to the Isoelectronic CpCr(CO)₃H