TY - JOUR
T1 - A detailed study of CHB bridge bonding in the simplest carborane
T2 - H2C(H2)BH2+
AU - McDonald, Lisa E.
AU - Gellene, Gregory I.
N1 - Funding Information:
L. E. M. is grateful to the Clark Scholar Program of Texas Tech University for a summer fellowship. Acknowledgement is made to the Robert A. Welch Foundation and the Petroleum Research Fund administered by the American Chemical Society for partial support of this work.
PY - 2001/3/10
Y1 - 2001/3/10
N2 - The structure, energetics, and bonding of the simplest carborane, H2C(H2)BH2+, is determined by high level ab initio calculations. The molecule is bound by 35.5 kcal mol-1 with respect to the lowest energy dissociation products, CH4 + BH2+, which are produced without a dissociation barrier (i.e. no reverse activation energy) along the minimum energy pathway. A detailed analysis of the occupied valence orbitals shows that the bonding arises from three-centre-two-electron bonding through an unusual carbon-hydrogen-boron (CHB) bridge bond explaining the strong binding energy and the absence of a dissociation barrier. The possibility that CHB bridge bonds may play a role in CH sigma bond activation is discussed. Harmonic vibrational frequencies, infrared absorption intensities, and frequency shifts occurring for 10B, 13C, and D isotopic substitution are reported.
AB - The structure, energetics, and bonding of the simplest carborane, H2C(H2)BH2+, is determined by high level ab initio calculations. The molecule is bound by 35.5 kcal mol-1 with respect to the lowest energy dissociation products, CH4 + BH2+, which are produced without a dissociation barrier (i.e. no reverse activation energy) along the minimum energy pathway. A detailed analysis of the occupied valence orbitals shows that the bonding arises from three-centre-two-electron bonding through an unusual carbon-hydrogen-boron (CHB) bridge bond explaining the strong binding energy and the absence of a dissociation barrier. The possibility that CHB bridge bonds may play a role in CH sigma bond activation is discussed. Harmonic vibrational frequencies, infrared absorption intensities, and frequency shifts occurring for 10B, 13C, and D isotopic substitution are reported.
UR - http://www.scopus.com/inward/record.url?scp=0035836320&partnerID=8YFLogxK
U2 - 10.1080/00268970010013986
DO - 10.1080/00268970010013986
M3 - Article
AN - SCOPUS:0035836320
VL - 99
SP - 377
EP - 382
JO - Molecular Physics
JF - Molecular Physics
SN - 0026-8976
IS - 5
ER -