Abstract
The geometric and electronic structure of formally d^6^ tris‐biphosphinine [M(bp)~3~]^q^ and tris‐bipyridine [M(bpy)~3~]^q^ complexes were studied by means of DFT calculations with the B3LYP functional. In agreement with the available experimental data, Group 4 dianionic [M(bp)~3~]^2−^ complexes (1P–3P for M=Ti, Zr, and Hf, respectively) adopt a trigonal‐prismatic (TP) structure, whereas the geometry of their nitrogen analogues [M(bpy)~3~]^2−^ (1N–3N) is nearly octahedral (OC), although a secondary minimum was found for the TP structures (1N′–3N′). The electronic factors at work in these systems are discussed by means of an MO analysis of the minima, MO correlation diagrams, and thermodynamic cycles connecting the octahedral and trigonal‐prismatic limits. In all these complexes, pronounced electron transfer from the metal center to the lowest lying π* ligand orbitals makes the d^6^ electron count purely formal. However, it is shown that the bp and bpy ligands accommodate the release of electron density from the metal in different ways because of a change in the localization of the HOMO, which is a mainly metal‐centered orbital in bp complexes and a pure π* ligand orbital in bpy complexes. The energetic evolution of the HOMO allows a simple rationalization of the progressive change from the TP to the OC structure on successive oxidation of the [Zr(bp)~3~]^2−^ complex, a trend in agreement with the experimental structure of the monoanionic complex. The geometry of Group 6 neutral complexes [M(bp)~3~] (4P and 5P for M=Mo and W, respectively) is found to be intermediate between the TP and OC limits, as previously shown experimentally for the tungsten complex. The electron transfer from the metal center to the lowest lying π* ligand orbitals is found to be significantly smaller than for the Group 4 dianionic analogues. The geometrical change between [Zr(bp)~3~]^2−^ and [W(bp)~3~] is analyzed by means of a thermodynamic cycle and it is shown that a larger ligand–ligand repulsion plays an important role in favoring the distortion of the tungsten complex away from the TP structure.