High-level, correlated electronic structure calculations on H3PS- and H3PSH indicate these two radicals to adopt trigonal bipyramidal geometries in which the unpaired electron is localized equatorially, although for the neutral species only the equatorially oriented mercaptan is stable to PS bond homolysis. The two radicals are otherwise fairly similar in both structure and predicted isotropic hyperfine splittings. Moreover, stereomutations on the H3PSH hypersurface are analogous to those predicted for H3POH.
Bibliographical noteFunding Information:
This work was supported in part by the Minnesota Supercomputer Institute. I am particularly grateful to Dr. Rent Janssen and Dr. Olav Aagaard for stimulating correspondence.