Abstract
Rhodium boryl complexes are valuable catalysts for hydro- or diboration reactions of alkenes, but can also react with ketones (R2C=O) and imines (R2C=NR′) giving rise to insertion products having formally Rh–R2C–O/NR′–B linkages. The resulting molecular structures, however, may show complex metal–ligand and ligand–ligand interaction patterns with often unclear metal–ligand connectivities (hapticities, ηn). In order to assign the correct hapticity in a set of asymmetric rhodium-allyl compounds with molecular structures indicating η1−5 bonding, a comprehensive DFT study was conducted. The study comprises determination of a variety of real-space bonding indicators derived from computed electron and pair densities according to the AIM, ELI-D, NCI, and DORI topological and surface approaches, which uncover the metal–ligand connectivties and suggest an asymmetric ligand–metal donation/metal–ligand back-donation framework according to the Dewar–Chatt–Duncanson model.
Theoretical design of new organic compounds based on diketopyrrolopyrrole and phenyl for organic bulk heterojunction solar cell applications: DFT and TD-DFT study
