New rhodium(III)-ED3AP complex: Crystal structure, characterization and computational chemistry

Only one (trans(O-5)-Na[Rh(ED3AP)]center dot 3H(2)O) of possible two isomers was synthesized and characterized by single crystal X-ray analysis, IR and UV-Vis spectroscopy. Computational analysis of both isomers was performed with three levels of theory (B3LYP/TZV, BP86/TZV, OPBE/TZV), which gave consistent results. The more stable isomer by total energy and ligand field stabilization energy (LFSE) was trans(O-5) which appeared in synthesis. The calculation of excited state energies complied with UV-Vis spectra, especially with OPBE functional. The results of excited state energy pointed out the dif-ferences among isomers in means of a splitting pattern of (1)T(2)g excited state term. Both isomers have a strongly delocalized structure, according to the nat-ural bonding orbital (NBO) analysis. The trans(O5) geometry has the stabiliz-ation of the whole system for roughly 87 kJ/mol and makes this isomer as the only one present in the reaction mixture.