The high covalence of metal-ligand bonds as stability limiting factor: the case of Rh(IX)O4+ and Rh(IX)NO3.

Rhodium, a 4d transition metal and a lighter analogue of iridium, is known to exhibit its highest VIth oxidation state in RhF6 molecule. In this report, the stability and decomposition pathways of two species containing rhodium at a potentially formal +IX oxidation state, [RhO4]+ and RhNO3, have been investigated theoretically within the framework of the relativistic two-component Hamiltonian calculations. Possible rearrangement into isomers featuring lower formal oxidation numbers has been explored. We found that both species studied are metastable with respect to elimination of O2 or NO. However, the local minima containing Rh(IX) are protected by sufficient energy barriers on the decomposition pathway, and they could in principle be prepared. The analysis of a broader set of compounds containing group 8 and 9 metals in high formal oxidation states that correspond to the group number showed that, in contrast to a standard trend, the limits of formally attainable oxidation state correlate with high level of covalent bonding character in the complexes studied.