Cr-Cr Quintuple Bonds: Ligand Topology and Interplay Between Metal-Metal and Metal-Ligand Bonding

Chromium-chromium quintuple bonds seem to be approaching the lower limit for their bond distances, and this computational density functional theory study tries to explore the geometrical and electronic factors that determine that distance and to find ways to fine-tune it via the ligand choice. While for monodentate ligands the Cr-Cr distance is predicted to shorten as the Cr-Cr-L bond angle increases, with bridging bidentate ligands the trend is the opposite, since those ligands with a larger number of spacers between the donor atoms favor larger bond angles and longer bond distances. Compared to Cr-Cr quadruple bonds, the quintuple bonding in Cr2L2 compounds (with L a bridging bidentate N-donor ligand) involves a sophisticated mechanism that comprises a positive pyramidality effect for the sigma and one pi bond, but a negative effect for one of the delta bonds. Moreover, the shorter Cr-Cr distances produce a mismatch of the bridging ligand lone pairs and the metal acceptor orbitals, which results in a negative correlation of the Cr-Cr and Cr-N bond distances in both experimental and calculated structures.