Journal of Physical Chemistry A, Vol.110, No.32, 9959-9966, 2006
An ab initio study of N-15-B-11 spin-spin coupling constants for borazine and selected derivatives
Ab initio equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) calculations have been performed to investigate substituent effects on coupling constants for borazine and selected substituted borazines. For molecules in which F atoms are not bonded to adjacent atoms in the ring, F substitution increases the one-bond B-11-N-15 coupling constants involving the atom at which substitution occurs but leaves the remaining one-bond B-N coupling constants essentially unchanged. For these molecules, the magnitudes of one-bond B-N coupling constants are only slightly dependent on the number of F atoms present. Fluorine substitution at adjacent B and N atoms in the borazine ring further increases the one-bond B-N coupling constant involving the substituted atoms and has the same effect on the other one-bond coupling constants as observed for corresponding molecules in which substitution occurs at alternate sites. In contrast to the effect of F substitution, substitution of Li at either N or B decreases one- bond B-N coupling constants relative to borazine. The effects of F and Li substitution on one-bond B-N coupling constants for borazine are similar to F and Li substitution effects on C-13-C-13 coupling constants for benzene.