Molecular and Electronic Structures of Mononuclear and Dinuclear Titanium Complexes Containing π-Radical Anions of 2,2'-Bipyridine and 1,10-Phenanthroline: An Experimental and DFT Computational Study.

Whereas reaction of (η(5)-Cp*)Ti(IV)Cl3 (1) with 2 equiv of neutral 2,2'-bipyridine (bpy) and 1.5 equiv of magnesium in tetrahydrofuran affords the mononuclear complex (η(5)-Cp*)Ti(III)(bpy(•))2 (2), performing the same reaction with only 1 equiv each of magnesium and bpy provides the dinuclear complex {(η(5)-Cp*)Ti(μ-Cl)(bpy(•))}2 (3). Conducting the latter reaction using 1,10-phenanthroline (phen) in place of bpy resulted in formation of dinuclear {(η(5)-Cp*)Ti(μ-Cl)(phen(•))}2 (4). The structures of 2, 3, and 4 have all been determined by high-resolution X-ray crystallography at 153 K; the Cpy-Cpy distances of 1.420(3) and 1.431(4) Å in the N,N'-coordinated bpy ligands of 2 and 3, respectively, are indicative of the presence of (bpy(•))(1-) ligands, rather than neutral (bpy(0)). The electronic spectra (300-1600 nm) of these two complexes are similar in form, and contain intense π → π* transitions associated with the (bpy(•))(1-) radical anion. Temperature dependent magnetic susceptibility measurements (4-300 K) show that mononuclear 2 possesses a temperature independent magnetic moment of 1.73 μB, which is indicative of an S = (1)/2 ground state. Broken symmetry density functional theory (BS-DFT) calculations yield a picture consistent with the experimental findings, in which the central Ti atom possesses a +3 oxidation state and is coordinated by a η(5)-Cp* ligand and two (bpy(•))(1-). Strong intramolecular antiferromagnetic coupling of these three unpaired spins, one each on the Ti(III) center and on the two (bpy(•))(1-) ligands, affords the experimentally observed doublet ground state. The magnetic susceptibility measurements for dinuclear 3 and 4 display weak but significant ferromagnetic coupling, and indicate that these complexes possess S = 1 ground states. The mechanism of the spin coupling phenomenon that yields the observed behavior was analyzed using BS-DFT calculations, and it was discovered that the tight π-stacking of the N,N'-coordinated (bpy(•))(1-)/(phen(•))(1-) ligands in these two complexes results from direct overlap of their SOMOs and formation of a two-electron multicentered bond. This yields a diamagnetic {(bpy)2}(2-)/{(phen)2}(2-) bridging unit whose doubly occupied HOMO is spread equally over both ligands. The two remaining unpaired electrons, one at each Ti(III) center, couple weakly in a ferromagnetic fashion to yield the experimentally observed S = 1 ground states.