Andrea E. Dorigo

Transition structures for H2 elimination from XH4 hypervalent species (X = S, Se and Te). Ab initio MO study

Abstract Ab initio MO calculations on the fragmentation of hypervalent XH4 (X = Se and Te) to XH2 and H2 show that the most favorable transition structure is highly polarized with C1 symmetry, which can be viewed as a trigonal bipyramid where one apical and one equatorial ligand are coupled. The least-motion C2v transition state previously obtained theoretically is much higher in energy.

Design, synthesis, and comparison of crystal, solution, and calculated structures within a new family of cavitands

A new family of cavitands based on [1.1.1]orthocyclophane has been designed and synthesized, one member of which provided crystal, solution, and calculated structures that are almost identical.

Theoretical studies of the role of complexation in the conjugate addition of dialkylcuprates to electron-deficient CC bonds. Influence on the stereochemistry of the reaction

Ab initio molecular orbital calculations suggest that dialkylcuprates add to conjugated CC bonds via a mechanism which involves pre-complexation of the copper centre with the double bond, implying an acute angle of attack onto the CC bond; this may explain the opposite stereoselectivities observed in the reactions of dialkylcuprates on the one hand and of alkylcopper reagents (and other conventional nucleophiles) on the other.