A computational and conceptual density functional theory study of the properties of Re and Tc tricarbonyl complexes

A computational and conceptual density functional study has been performed on metal tricarbonyl complexes (MTC) of both Re(I) and Tc(I). The fully optimized complexes of fac-[Tc(OH2)(CO3)](+) and mer-[Tc(OH2)(CO3)]+ show geometries that compare favorably with the X-ray data. These structures were used as a starting point to investigate the relative stability of MTC complexes with various ligands containing combinations of N, O, and S as chelating atoms and to evaluate the stabilizing/destabilizing influence of these ligands. Both for Tc and for Re complexes the nitrogen content turns out to be decisive in the stability of the metaltricarbonyl complexes, the finer details being determined by the hardness sequence N > O > S. As the core of the complexes, [( M(CO)(3)(+)], is hard, the main ordering parameter is changed as compared to our previous studies on Tc(V) [3+1] complexes where the number of sulfur atoms was decisive in accordance with the much softer character of the MOCl core. All results are successfully interpreted in terms of the hard and soft acids and bases principle ( HSAB) at the local level.