Prediction of heptagonal bipyramidal nonacoordination in highly viable [OB-M©B7O7-BO]- (M = Fe, Ru, Os) complexes

Non-spherical distributions of ligand atoms in coordination complexes are generally unfavorable due to higher repulsion than for spherical distributions. To the best of our knowledge, non-spherical heptagonal bipyramidal nonacoordination is hitherto unreported, because of extremely high repulsion among seven equatorial ligand atoms. Herein, we report the computational prediction of such nonacoordination, which is constructed by the synergetic coordination of an equatorial hepta-dentate centripetal ligand (B7O7) and two axial mono-dentate ligands (-BO) in the gear-like mono-anionic complexes [OB-M (c) B7O7-BO](-) (M = Fe, Ru, Os). The high repulsion among seven equatorial ligand B atoms has been compensated by the strong B-O bonding. These complexes are the dynamically stable (up to 1500 K) global energy minima with the HOMO-LUMO gaps of 7.15 to 7.42 eV and first vertical detachment energies of 6.14 to 6.66 eV (being very high for anions), suggesting their high probability for experimental realization in both gas-phase and condensed phases. The high stability stems geometrically from the surrounded outer-shell oxygen atoms and electronically from meeting the 18e rule as well as possessing the sigma + pi + delta triple aromaticity. Remarkably, the ligand-metal interactions are governed not by the familiar donation and backdonation interactions, but by the electrostatic interactions and electron-sharing bonding. Complexes possessing coordination spheres that can accommodate nine ligand atoms typically display spherical distributions of these atoms. Here, the authors predict that M-centered [OB-B7O7-BO] adopts unusual heptagonal bipyramidal nonacoordination.

Automated summary

The study reports a novel non-spherical coordination structure, demonstrating that the high repulsion among seven equatorial ligand atoms in a heptagonal bipyramidal nonacoordination system can be compensated by the strength of B-O bonding, leading to dynamic stability and high experimental realization potential.