Solution homolytic bond dissociation energies of organotransition-metal hydrides

Tilset, Mats; Parker, Vernon D.

doi:10.1021/ja00199a034

Cited by 243 publications

(191 citation statements)

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“…Þ is the heterolysis standard free energy, the acid-dissociation standard free energy, and the hydricity of H 2 , and is assigned a value of 76 kcal∕mol in acetonitrile by DuBois and others (18,19). This is a difficult quantity to calculate or to measure because it involves the solvation of both the gas-phase proton and the gasphase hydride ion.…”

Section: Modelmentioning

confidence: 99%

Calculation of thermodynamic hydricities and the design of hydride donors for CO ₂ reduction

Muckerman

Achord

Creutz

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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We have developed a correlation between experimental and density functional theory-derived results of the hydride-donating power, or “hydricity”, of various ruthenium, rhenium, and organic hydride donors. This approach utilizes the correlation between experimental hydricity values and their corresponding calculated free-energy differences between the hydride donors and their conjugate acceptors in acetonitrile, and leads to an extrapolated value of the absolute free energy of the hydride ion without the necessity to calculate it directly. We then use this correlation to predict, from density functional theory-calculated data, hydricity values of ruthenium and rhenium complexes that incorporate the pbnHH ligand—pbnHH = 1,5-dihydro-2-(2-pyridyl)-benzo[ b ]-1,5-naphthyridine—to model the function of NADPH. These visible light-generated, photocatalytic complexes produced by disproportionation of a protonated-photoreduced dimer of a metal-pbn complex may be valuable for use in reducing CO 2 to fuels such as methanol. The excited-state lifetime of photoexcited [Ru(bpy) 2 (pbnHH)] 2+ is found to be about 70 ns, and this excited state can be reductively quenched by triethylamine or 1,4-diazabicyclo[2.2.2]octane to produce the one-electron-reduced [Ru(bpy) 2 (pbnHH)] + species with half-life exceeding 50 μs, thus opening the door to new opportunities for hydride-transfer reactions leading to CO 2 reduction by producing a species with much increased hydricity.

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Section: Modelmentioning

confidence: 99%

Calculation of thermodynamic hydricities and the design of hydride donors for CO ₂ reduction

Muckerman

Achord

Creutz

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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“…This property is equivalent to the BDE of the OOH bond that is formed, which is a function of both the redox potential of the MAO oxidant and the pK a of the nascent OOH bond based on a thermochemical cycle developed by Bordwell et al (45) and others (46)(47)(48). Thus, a less favorable redox potential can be energetically compensated for by a higher pK a .…”

Section: The Reactivity Of [Fe(iv)(o)(tmcs)] ؉ (1 -Sr)mentioning

confidence: 99%

Axial ligand tuning of a nonheme iron(IV)–oxo unit for hydrogen atom abstraction

Sastri

Lee

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

384

449

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“…Tilset and Parker have described how metal-hydride bond dissociation energies, AHBDE(MH), of complexes MHL, can be determined by measuring the pK, of the hydride complex, pKa(MHL5) and the electrochemical potential of the conjugate base hydride, EI,2(ML,IML5-) (31,32). We made use of an identical thermochemical cycle to determine the bond dissociation energies (BDE) for dihydrogen complexes, MH2L5 (eqs.…”

Section: The H-atom Abstraction Energy Ah{m(h)) As An Indicator mentioning

confidence: 99%

1995 Alcan Award Lecture New intermediates in the homolytic and heterolytic splitting of dihydrogen

Morris¹

1996

Can. J. Chem.

107

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Some of the research of the author and his research group into the structure and reactions of dihydrogen complexes of transition metals is reviewed. The characterization of osmium complexes that can be regarded as having intermediate structures on the way to the homolytic splitting and to the heterolytic splitting of dihydrogen is described. The properties of an iridium complex with novel short proton-hydride contacts is also reviewed.Ke)) words: transition metal, dihydrogen, hydride, complexes, NMR, neutron diffraction, osmium, iridium.Resume : On prCsente une revue des travaux de recherche effectuCs dans les laboratoires de l'auteur sur la structure et les rCactions des complexes dihydrogCnCs des mCtaux de transition. On dCcrit la caracterisation des complexes de l'osmium qui peuvent &tre considCrCs comme possCdant des structures intermediaires entre celles conduisant aux ruptures de la liaison H-H du dihydrogkne soit homolytiques soit hCtCrolytiques. On passe aussi en revue les propriCtCs d'un complexe d'iridium qui comporte de nouveaux contacts courts hydrons-hydrure.

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Solution homolytic bond dissociation energies of organotransition-metal hydrides

Cited by 243 publications

References 0 publications

Calculation of thermodynamic hydricities and the design of hydride donors for CO ₂ reduction

Calculation of thermodynamic hydricities and the design of hydride donors for CO ₂ reduction

Axial ligand tuning of a nonheme iron(IV)–oxo unit for hydrogen atom abstraction

1995 Alcan Award Lecture New intermediates in the homolytic and heterolytic splitting of dihydrogen

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Solution homolytic bond dissociation energies of organotransition-metal hydrides

Cited by 243 publications

References 0 publications

Calculation of thermodynamic hydricities and the design of hydride donors for CO 2 reduction

Calculation of thermodynamic hydricities and the design of hydride donors for CO 2 reduction

Axial ligand tuning of a nonheme iron(IV)–oxo unit for hydrogen atom abstraction

1995 Alcan Award Lecture New intermediates in the homolytic and heterolytic splitting of dihydrogen

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Calculation of thermodynamic hydricities and the design of hydride donors for CO ₂ reduction

Calculation of thermodynamic hydricities and the design of hydride donors for CO ₂ reduction