The phosphonate-phosphate rearrangement is an isomerisation of α-hydroxyphosphonates bearing electron-withdrawing substituents at the α-carbon atom. We studied the stereochemical course of this rearrangement with respect to phosphorus. A set of four diastereomeric α-hydroxyphosphonates was prepared by a Pudovik reaction from two diastereomeric cyclic phosphites. The hydroxyphosphonates were sep...

A framework is formulated for the development of a predictive structure-activity relationship for the temperature-dependent rate coefficients of H-migration in substituted alkoxy radicals. It is based on a multi-conformer transition state theory model, using quantum chemical characterizations of alkoxy radicals and their transition states for isomerisation. Using this framework, a SAR is then d...

Novel p-block metallacarboranes with 4,1,10-SnC2B10 and 4,1,12-SnC2B10 architectures are described; the structures of bipyridyl adducts of these compounds reveal very different bipyridyl orientations yielding unique experimental information on the relative trans influences of facial B and C atoms in the cage.