Bond Energy and Other Properties of the Re-Re Quadruple Bond

David C. Smith; William A. Goddard

doi:10.1021/ja00253a003

Bond Energy and Other Properties of the Re-Re Quadruple Bond

David C. Smith
, William A. Goddard

California Institute of Technology

Research output: Contribution to journal › Article › peer-review

Abstract

Using generalized valence bond (GVB) methods designed for obtaining accurate bond energies, we predict an Re-Re quadruple bond strength of 85 ± 5 kcal/mol for Re₂Cl₈¹^{2 3}⁴”. This is much less than early estimates of 370 kcal/mol and somewhat lower than estimates (124 to 150 kcal/mol) based on Birge-Sponer extrapolation but is in reasonable agreement with a recent thermochemical study (97 ± 12 kcal/mol). We obtain a rotational barrier of 3.0 kcal/mol and a singlet-triplet excitation energy of 3100 cm^-1, and we conclude that the intrinsic strength of the <5 bond is 6 ± 3 kcal/mol.

Original language	English
Pages (from-to)	5580-5583
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	109
Issue number	19
DOIs	https://doi.org/10.1021/ja00253a003
Publication status	Published - 1 Sept 1987
Externally published	Yes

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title = "Bond Energy and Other Properties of the Re-Re Quadruple Bond",

abstract = "Using generalized valence bond (GVB) methods designed for obtaining accurate bond energies, we predict an Re-Re quadruple bond strength of 85 ± 5 kcal/mol for Re2Cl812 34”. This is much less than early estimates of 370 kcal/mol and somewhat lower than estimates (124 to 150 kcal/mol) based on Birge-Sponer extrapolation but is in reasonable agreement with a recent thermochemical study (97 ± 12 kcal/mol). We obtain a rotational barrier of 3.0 kcal/mol and a singlet-triplet excitation energy of 3100 cm-1, and we conclude that the intrinsic strength of the <5 bond is 6 ± 3 kcal/mol.",

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T1 - Bond Energy and Other Properties of the Re-Re Quadruple Bond

AU - Smith, David C.

AU - Goddard, William A.

PY - 1987/9/1

Y1 - 1987/9/1

N2 - Using generalized valence bond (GVB) methods designed for obtaining accurate bond energies, we predict an Re-Re quadruple bond strength of 85 ± 5 kcal/mol for Re2Cl812 34”. This is much less than early estimates of 370 kcal/mol and somewhat lower than estimates (124 to 150 kcal/mol) based on Birge-Sponer extrapolation but is in reasonable agreement with a recent thermochemical study (97 ± 12 kcal/mol). We obtain a rotational barrier of 3.0 kcal/mol and a singlet-triplet excitation energy of 3100 cm-1, and we conclude that the intrinsic strength of the <5 bond is 6 ± 3 kcal/mol.

AB - Using generalized valence bond (GVB) methods designed for obtaining accurate bond energies, we predict an Re-Re quadruple bond strength of 85 ± 5 kcal/mol for Re2Cl812 34”. This is much less than early estimates of 370 kcal/mol and somewhat lower than estimates (124 to 150 kcal/mol) based on Birge-Sponer extrapolation but is in reasonable agreement with a recent thermochemical study (97 ± 12 kcal/mol). We obtain a rotational barrier of 3.0 kcal/mol and a singlet-triplet excitation energy of 3100 cm-1, and we conclude that the intrinsic strength of the <5 bond is 6 ± 3 kcal/mol.

UR - https://www.scopus.com/pages/publications/33845281485

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DO - 10.1021/ja00253a003

M3 - Article

AN - SCOPUS:33845281485

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SP - 5580

EP - 5583

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 19

ER -

Bond Energy and Other Properties of the Re-Re Quadruple Bond

Abstract

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