Ring-whizzing in polyene-PtL2 complexes revisited

Abstract

Ring-whizzing was investigated by hybrid DFT methods in a number of polyene–Pt(diphosphinylethane) complexes. The polyenes included cyclopropenium+, cyclobutadiene, cyclopentadienyl+, hexafluorobenzene, cycloheptatrienyl+, cyclooctatetraene, octafluorooctatetraene, 6-radialene, pentalene, phenalenium+, naphthalene and octafluoronaphthalene. The HOMO of a d10 ML2 group (with b2 symmetry) interacting with the LUMO of the polyene was used as a model to explain the occurrence of minima and maxima on the potential energy surface.

Keywords

• d10 metal complexes
• density functional theory (DFT)
• hapototropic rearrangements
• HOMO–LUMO interactions
• polyene-ML2 complexes
• ring-whizzing