A Computational Characterization of Boron−Oxygen Multiple Bonding in HN=CH−CH=CH−NH−BO

Joseph D Larkin, Krishna L Bhat, George D Markham, Tony D James, Bernard R Brooks, Charles W Bock

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Abstract

H=CH-NH-BO,and the corresponding borocycle (-HN=CH-CH=CH-NH-B-)O are discussed using results from second-order Moller-Plesset (MP2) perturbation theory with the Dunning-Woon correlation-consistent cc-pVDZ, aug-cc-pVDZ, and cc-pVTZ basis sets. These MP2 results are compared to those from computationally efficient density functional theory (DFT) calculations using the LDA, PBE, TPSS, BLYP, B3LYP. BVP86, OLYP, O3LYP, and PBE1PBE functionals in conjunction with the economical Pople-type 6-311 ++G(d,p) basis set to evaluate the suitability of these DFT/6-311 ++G(d,p) levels for use With larger boron-containing systems. The effects of an aqueous environment were incorporated into the calculations using COSMO methodology. The calculated boron-oxygen bond lengths, orbital compositions, and bond orders in all the (acyclic) HN=CH-CH=CH-NH-BO conformers were consistent with the presence of a boron-oxygen triple bond, similar to that found in H-B O and H2N-B O. The (-HN=CH-CH=CH-NH-B-)O borocycle is predicted to be planar (C,, symmetry), and it is similar to 30 kcal/mol lower in energy than any of the (acyclic) HN=CH-CH=CH-NH-BO conformers; the boron-oxygen bond in this borocycle has significant double bond character, a bonding scheme for which there has been only one experimental structure reported in the literature (Vidovic, D.; et al. J. Am. Chem. Soc. 2005, 127, 4566-4569).
Original languageEnglish
Pages (from-to)8446-8454
Number of pages9
JournalThe Journal of Physical Chemistry A
Volume112
Issue number36
DOIs
Publication statusPublished - 2008

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Boron
boron
methylidyne
Oxygen
oxygen
Density functional theory
Bond length
Chemical analysis
density functional theory
functionals

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A Computational Characterization of Boron−Oxygen Multiple Bonding in HN=CH−CH=CH−NH−BO. / Larkin, Joseph D; Bhat, Krishna L; Markham, George D; James, Tony D; Brooks, Bernard R; Bock, Charles W.

In: The Journal of Physical Chemistry A, Vol. 112, No. 36, 2008, p. 8446-8454.

Research output: Contribution to journalArticle

Larkin, Joseph D ; Bhat, Krishna L ; Markham, George D ; James, Tony D ; Brooks, Bernard R ; Bock, Charles W. / A Computational Characterization of Boron−Oxygen Multiple Bonding in HN=CH−CH=CH−NH−BO. In: The Journal of Physical Chemistry A. 2008 ; Vol. 112, No. 36. pp. 8446-8454.
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abstract = "H=CH-NH-BO,and the corresponding borocycle (-HN=CH-CH=CH-NH-B-)O are discussed using results from second-order Moller-Plesset (MP2) perturbation theory with the Dunning-Woon correlation-consistent cc-pVDZ, aug-cc-pVDZ, and cc-pVTZ basis sets. These MP2 results are compared to those from computationally efficient density functional theory (DFT) calculations using the LDA, PBE, TPSS, BLYP, B3LYP. BVP86, OLYP, O3LYP, and PBE1PBE functionals in conjunction with the economical Pople-type 6-311 ++G(d,p) basis set to evaluate the suitability of these DFT/6-311 ++G(d,p) levels for use With larger boron-containing systems. The effects of an aqueous environment were incorporated into the calculations using COSMO methodology. The calculated boron-oxygen bond lengths, orbital compositions, and bond orders in all the (acyclic) HN=CH-CH=CH-NH-BO conformers were consistent with the presence of a boron-oxygen triple bond, similar to that found in H-B O and H2N-B O. The (-HN=CH-CH=CH-NH-B-)O borocycle is predicted to be planar (C,, symmetry), and it is similar to 30 kcal/mol lower in energy than any of the (acyclic) HN=CH-CH=CH-NH-BO conformers; the boron-oxygen bond in this borocycle has significant double bond character, a bonding scheme for which there has been only one experimental structure reported in the literature (Vidovic, D.; et al. J. Am. Chem. Soc. 2005, 127, 4566-4569).",
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AU - Bock, Charles W

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AB - H=CH-NH-BO,and the corresponding borocycle (-HN=CH-CH=CH-NH-B-)O are discussed using results from second-order Moller-Plesset (MP2) perturbation theory with the Dunning-Woon correlation-consistent cc-pVDZ, aug-cc-pVDZ, and cc-pVTZ basis sets. These MP2 results are compared to those from computationally efficient density functional theory (DFT) calculations using the LDA, PBE, TPSS, BLYP, B3LYP. BVP86, OLYP, O3LYP, and PBE1PBE functionals in conjunction with the economical Pople-type 6-311 ++G(d,p) basis set to evaluate the suitability of these DFT/6-311 ++G(d,p) levels for use With larger boron-containing systems. The effects of an aqueous environment were incorporated into the calculations using COSMO methodology. The calculated boron-oxygen bond lengths, orbital compositions, and bond orders in all the (acyclic) HN=CH-CH=CH-NH-BO conformers were consistent with the presence of a boron-oxygen triple bond, similar to that found in H-B O and H2N-B O. The (-HN=CH-CH=CH-NH-B-)O borocycle is predicted to be planar (C,, symmetry), and it is similar to 30 kcal/mol lower in energy than any of the (acyclic) HN=CH-CH=CH-NH-BO conformers; the boron-oxygen bond in this borocycle has significant double bond character, a bonding scheme for which there has been only one experimental structure reported in the literature (Vidovic, D.; et al. J. Am. Chem. Soc. 2005, 127, 4566-4569).

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