Substituents effect on the electronic structure and molecular properties of bis[organohydrazido(2−)] molybdenum(VI) complexes

Two related families of molybdenum complexes of the form [MoBr2L(NNR1R2)2], where L = 2,2′-bipyridine (bipy) or ortho-phenanthroline (o-phen) and NNR1R2 = N,N substituted hydrazido(2−) ligands where R1 and R2 correspond to methyl and/or phenyl groups. The derivatives have been fully theoretically characterized, carrying on the geometrical characterization of molecular structure, energy decomposition analysis (EDA) and calculation of the absorption spectra using TD-DFT. The study has been performed using Density Functional Theory (DFT), using LDA and GGA(PW91 and BP86) functionals, with the TZP slater type basis set. We found that the complexes are isostructural, have a very similar orbital composition and also show very similar energy values for the frontier molecular orbitals (FMO), except in case of the LUMO+1 which exhibit a special behaviour. The calculated excitations energies are in agreement with the previously reported experimental data. Due to the good agreement between the experimental and theoretical report, a proposal of not yet synthesized complexes was performed.

Substituents effect on the electronic structure and molecular properties of bis[organohydrazido(2−)] molybdenum and a detailed theoretical study of the EDA.Figure optionsDownload as PowerPoint slide