Theoretical investigations on electronics structure and chemical bonding on iridathiabenzene and iridaoxabenzene

The electronic structure and properties of the iridathiabenzene and iridaoxabenzene isomers have been investigated using the hybrid density functional mpw1pw91 theory. The energetic aspect shows that trans-ortho-isomer is the most stable isomer. This is compatible with principles of minimum energy and minimum polarizability. Molecular orbital analysis shows a linear correlation between hardness and anisotropic polarizability values for Iridathiabenzene and iridaoxabenzene isomers. The structural and natural bond analysis (NBO) results illustrate electronic delocalization in these rings. Also, the study of non linear optical properties of these molecules indicate a good correlation between β_tot and E(HOMO) for iridathiabenzene. The results from natural bond orbital (NBO) analysis have provided insights into Ir—ligand, P—H_apical and P—H_basal bonding.