ANALYSIS OF THE THROUGH-BOND INTERACTION USING THE LOCALIZED MOLECULAR-ORBITALS .2. LONG-RANGE PROTON HYPERFINE COUPLING IN BRIDGEHEAD ALKYL RADICALS - BICYCLO[1.1.1]PENT-1-YL, BICYCLO[2.1.1]HEX-1-YL AND BICYCLO[2.2.1]HEPT-1-YL RADICALS

The INDO calculations were performed on three bridgehead alkyl radicals; bicyclo[1.1.1]pent-1-yl, bicyclo[2.1.1]hex-l-yl and bicyclo[2.2.1]hept-1-yl radicals. We have transformed the canonical molecular orbitals obtained by the INDO method into the localized molecular orbitals. With the use of the obtained localized molecular orbitals, the variation in the hyperfine coupling constant at the bridgehead proton in these radicals was pursued in terms of the through-bond (and/or the through-space) interaction according to the method by which we selectively can pick up a particular interaction between the specified localized molecular orbitals in a radical. As a result of this analysis, it was found that the hyperfine coupling constants in these radicals can be expressed by the summation of several terms; through-virtuals, through-space, through-bond, and some other coupling terms. © 1979.