Ab initio characterization of the isomerism between the μ-η2:η2-peroxo- and bis(μ-oxo)dicopper cores

Christopher J. Cramer; Bradley A. Smith; William B. Tolman

doi:10.1021/ja962455n

Ab initio characterization of the isomerism between the μ-η²:η²-peroxo- and bis(μ-oxo)dicopper cores

Christopher J. Cramer, Bradley A. Smith, William B. Tolman

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Abstract

The interconversion of model compounds {[(NH₃)₃Cu]₂(μ-η²:η²-O₂)}²⁺ (1) and {[(NH₃)₃Cu]₂(μ-O)₂}²⁺ (2) has been examined using multireference second-order perturbation theory with an 8-electron/8-orbital active space. At this level of theory, 1 and 2 are separated by only 0.3 kcal/mol, and the barrier to isomerization is predicted to be very low based on single-point energy calculations for intermediate structures. The flat nature of the potential energy surface along the interconversion coordinate derives from a balancing of Coulomb forces and nondynamic electron correlation. The latter effect depends critically on the significant energy change experienced by the 13a(u) σ(oo)* virtual orbital on passing from one isomer to the other. In addition, solvation electrostatics favor 2 over 1.

Original language	English (US)
Pages (from-to)	11283-11287
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	118
Issue number	45
DOIs	https://doi.org/10.1021/ja962455n
State	Published - Nov 13 1996

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title = "Ab initio characterization of the isomerism between the μ-η2:η2-peroxo- and bis(μ-oxo)dicopper cores",

abstract = "The interconversion of model compounds {[(NH3)3Cu]2(μ-η2:η2-O2)}2+ (1) and {[(NH3)3Cu]2(μ-O)2}2+ (2) has been examined using multireference second-order perturbation theory with an 8-electron/8-orbital active space. At this level of theory, 1 and 2 are separated by only 0.3 kcal/mol, and the barrier to isomerization is predicted to be very low based on single-point energy calculations for intermediate structures. The flat nature of the potential energy surface along the interconversion coordinate derives from a balancing of Coulomb forces and nondynamic electron correlation. The latter effect depends critically on the significant energy change experienced by the 13a(u) σ(oo)* virtual orbital on passing from one isomer to the other. In addition, solvation electrostatics favor 2 over 1.",

author = "Cramer, {Christopher J.} and Smith, {Bradley A.} and Tolman, {William B.}",

year = "1996",

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T1 - Ab initio characterization of the isomerism between the μ-η2:η2-peroxo- and bis(μ-oxo)dicopper cores

AU - Cramer, Christopher J.

AU - Smith, Bradley A.

AU - Tolman, William B.

PY - 1996/11/13

Y1 - 1996/11/13

N2 - The interconversion of model compounds {[(NH3)3Cu]2(μ-η2:η2-O2)}2+ (1) and {[(NH3)3Cu]2(μ-O)2}2+ (2) has been examined using multireference second-order perturbation theory with an 8-electron/8-orbital active space. At this level of theory, 1 and 2 are separated by only 0.3 kcal/mol, and the barrier to isomerization is predicted to be very low based on single-point energy calculations for intermediate structures. The flat nature of the potential energy surface along the interconversion coordinate derives from a balancing of Coulomb forces and nondynamic electron correlation. The latter effect depends critically on the significant energy change experienced by the 13a(u) σ(oo)* virtual orbital on passing from one isomer to the other. In addition, solvation electrostatics favor 2 over 1.

AB - The interconversion of model compounds {[(NH3)3Cu]2(μ-η2:η2-O2)}2+ (1) and {[(NH3)3Cu]2(μ-O)2}2+ (2) has been examined using multireference second-order perturbation theory with an 8-electron/8-orbital active space. At this level of theory, 1 and 2 are separated by only 0.3 kcal/mol, and the barrier to isomerization is predicted to be very low based on single-point energy calculations for intermediate structures. The flat nature of the potential energy surface along the interconversion coordinate derives from a balancing of Coulomb forces and nondynamic electron correlation. The latter effect depends critically on the significant energy change experienced by the 13a(u) σ(oo)* virtual orbital on passing from one isomer to the other. In addition, solvation electrostatics favor 2 over 1.

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Ab initio characterization of the isomerism between the μ-η²:η²-peroxo- and bis(μ-oxo)dicopper cores

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