Rhodium(i) complexes with carborane-substituted P,N ligands: investigations of electronic structure and dynamic behaviour

Dalton Trans. 2019 Jul 2;48(26):9625-9630. doi: 10.1039/c9dt00628a.


Two distorted square-planar RhI complexes (1 and 2) were obtained from [{RhCl(η4-cod)}2] and the respective P,N ligands. The metal-ligand interaction was probed with density functional theory (DFT) and ab initio (CASSCF-NEVPT2) calculations. NMR spectroscopy proved dynamic binding behaviour of the ligands in solution. The tetradenticity of the ligands also affects the electrochemical behaviour of complexes 1 and 2 significantly. Finally, preliminary catalytic studies, namely the dehydrocoupling of dimethylamine-borane, are presented.