Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

2003

Journal or Book Title

Organometallics

Volume

22

Issue

1

First Page

42

Last Page

46

DOI

10.1021/om020470x

Abstract

The nature of the multiple bonding of H2TiEH2 (E = C, Si) and H2TiEH (E = N, P) molecules has been investigated with the multiconfiguration SCF (MCSCF) method. It is shown that the Ti−C and Ti−P bond lengths decrease with bond rotation, whereas the Ti−Si bond length increases. MCSCF geometry optimization shows that Ti−N has triple-bond character with a linear Ti−N−H bond angle that results from strong back-bonding from the N lone pair into the empty Ti d orbitals. The rotation barrier and bond dissociation energy for TiE are estimated with the MCSCF + multireference second-order perturbation theory (MRMP2) method. The singlet rotation barriers in TiC, TiSi, and TiP are estimated to be 15.9, 8.6, and 9.3 kcal/mol, respectively. The TiC and TiSi bond dissociation energies are estimated to be 83.4 and 56.9 kcal/mol, respectively. The Ti⋮N triple-bond energy is about 30 kcal/mol larger than that of the carbon species, whereas the energy of the TiP bond is about 8 kcal/mol smaller than that of the silicon species.

Comments

Reprinted (adapted) with permission from Organometallics 22 (2003): 42, doi:10.1021/om020470x. Copyright 2003 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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