Transition state characterization for the reversible binding of dihydrogen to bis(2,2′-bipyridine)rhodium(I) from temperature- and pressure-dependent experimental and theoretical studies

Etsuko Fujita, Bruce S. Brunschwig, Carol Creutz, James Muckerman, Norman Sutin, David Szalda, Rudi Van Eldik

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Abstract

Thermodynamic and kinetic parameters for the oxidative addition of H 2 to [RhI(bpy)2]+ (bpy = 2,2′-bipyridine) to form [RhIII(H)2(bpy) 2]+ were determined from either the UV-vis spectrum of equilibrium mixtures of [RhI(bpy)2]+ and [RhIII(H)2(bpy)2]+ or from the observed rates of dihydride formation following visible-light irradiation of solutions containing [RhIII(H)2(bpy)2] + as a function of H2 concentration, temperature, and pressure in acetone and methanol. The activation enthalpy and entropy in methanol are 10.0 kcal mol-1 and -18 cal mol-1 K-1, respectively. The reaction enthalpy and entropy are -10.3 kcal mol-1 and -19 cal mol-1 K-1, respectively. Similar values were obtained in acetone. Surprisingly, the volumes of activation for dihydride formation (-15 and -16 cm3 mol-1 in methanol and acetone, respectively) are very close to the overall reaction volumes (-15 cm3 mol-1 in both solvents). Thus, the volumes of activation for the reverse reaction, elimination of dihydrogen from the dihydrido complex, are approximately zero. B3LYP hybrid DFT calculations of the transition-state complex in methanol and similar MP2 calculations in the gas phase suggest that the dihydrogen has a short H-H bond (0.823 and 0.810 Å, respectively) and forms only a weak Rh-H bond (1.866 and 1.915 Å, respectively). Equal partial molar volumes of the dihydrogenrhodium(I) transition state and dihydridorhodium(III) can account for the experimental volume profile found for the overall process.

Original languageEnglish
Pages (from-to)1595-1603
Number of pages9
JournalInorganic Chemistry
Volume45
Issue number4
DOIs
Publication statusPublished - Feb 20 2006

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Rhodium
rhodium
Methanol
Acetone
methyl alcohol
Chemical activation
acetone
dihydrides
activation
Enthalpy
Entropy
Temperature
enthalpy
temperature
entropy
Kinetic parameters
Discrete Fourier transforms
Density (specific gravity)
Gases
Irradiation

ASJC Scopus subject areas

  • Inorganic Chemistry

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Transition state characterization for the reversible binding of dihydrogen to bis(2,2′-bipyridine)rhodium(I) from temperature- and pressure-dependent experimental and theoretical studies. / Fujita, Etsuko; Brunschwig, Bruce S.; Creutz, Carol; Muckerman, James; Sutin, Norman; Szalda, David; Van Eldik, Rudi.

In: Inorganic Chemistry, Vol. 45, No. 4, 20.02.2006, p. 1595-1603.

Research output: Contribution to journalArticle

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abstract = "Thermodynamic and kinetic parameters for the oxidative addition of H 2 to [RhI(bpy)2]+ (bpy = 2,2′-bipyridine) to form [RhIII(H)2(bpy) 2]+ were determined from either the UV-vis spectrum of equilibrium mixtures of [RhI(bpy)2]+ and [RhIII(H)2(bpy)2]+ or from the observed rates of dihydride formation following visible-light irradiation of solutions containing [RhIII(H)2(bpy)2] + as a function of H2 concentration, temperature, and pressure in acetone and methanol. The activation enthalpy and entropy in methanol are 10.0 kcal mol-1 and -18 cal mol-1 K-1, respectively. The reaction enthalpy and entropy are -10.3 kcal mol-1 and -19 cal mol-1 K-1, respectively. Similar values were obtained in acetone. Surprisingly, the volumes of activation for dihydride formation (-15 and -16 cm3 mol-1 in methanol and acetone, respectively) are very close to the overall reaction volumes (-15 cm3 mol-1 in both solvents). Thus, the volumes of activation for the reverse reaction, elimination of dihydrogen from the dihydrido complex, are approximately zero. B3LYP hybrid DFT calculations of the transition-state complex in methanol and similar MP2 calculations in the gas phase suggest that the dihydrogen has a short H-H bond (0.823 and 0.810 {\AA}, respectively) and forms only a weak Rh-H bond (1.866 and 1.915 {\AA}, respectively). Equal partial molar volumes of the dihydrogenrhodium(I) transition state and dihydridorhodium(III) can account for the experimental volume profile found for the overall process.",
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T1 - Transition state characterization for the reversible binding of dihydrogen to bis(2,2′-bipyridine)rhodium(I) from temperature- and pressure-dependent experimental and theoretical studies

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N2 - Thermodynamic and kinetic parameters for the oxidative addition of H 2 to [RhI(bpy)2]+ (bpy = 2,2′-bipyridine) to form [RhIII(H)2(bpy) 2]+ were determined from either the UV-vis spectrum of equilibrium mixtures of [RhI(bpy)2]+ and [RhIII(H)2(bpy)2]+ or from the observed rates of dihydride formation following visible-light irradiation of solutions containing [RhIII(H)2(bpy)2] + as a function of H2 concentration, temperature, and pressure in acetone and methanol. The activation enthalpy and entropy in methanol are 10.0 kcal mol-1 and -18 cal mol-1 K-1, respectively. The reaction enthalpy and entropy are -10.3 kcal mol-1 and -19 cal mol-1 K-1, respectively. Similar values were obtained in acetone. Surprisingly, the volumes of activation for dihydride formation (-15 and -16 cm3 mol-1 in methanol and acetone, respectively) are very close to the overall reaction volumes (-15 cm3 mol-1 in both solvents). Thus, the volumes of activation for the reverse reaction, elimination of dihydrogen from the dihydrido complex, are approximately zero. B3LYP hybrid DFT calculations of the transition-state complex in methanol and similar MP2 calculations in the gas phase suggest that the dihydrogen has a short H-H bond (0.823 and 0.810 Å, respectively) and forms only a weak Rh-H bond (1.866 and 1.915 Å, respectively). Equal partial molar volumes of the dihydrogenrhodium(I) transition state and dihydridorhodium(III) can account for the experimental volume profile found for the overall process.

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