SPIN-STATE EQUILIBRIA IN NONAQUEOUS SOLUTION AND QUANTUM-MECHANICAL INVESTIGATIONS OF IRON(II) AND NICKEL(II) COMPLEXES WITH 4-SUBSTITUTED 2,6-BIS(BENZIMIDAZOL-2-YL)PYRIDINES

Cationic complexes with a series of tridentate ligands, L = 4X-substit uted 2,6-bis(benzimidazol-2-yl)-pyridines, [ML2][ClO4]2 (M = Fe or Ni; X = H, OH or Cl), were isolated and characterized, together with the free pyridines, by elemental analysis, Fourier-transform IR, H-1 NMR a nd UV/VIS spectroscopy. The syntheses were performed via condensation of o-phenylenediamine with 4-substituted pyridine-2,6-dicarboxylic aci ds. Ligand-field parameters were estimated for the nickel complexes. T he [FeL2]2+ species show thermally induced spin-crossover behaviour (1 A1 --> 5T2g) which has been investigated in methanol, nitromethane and 20% (v/v) dimethylformamide in MeOH. The behaviour is complicated by two complex dissociation equilibria, for which equilibrium constants h ave been evaluated. Ligand substitution is reflected in a change of th e spin state in solution [mu(exptl) = 2.50, X = H; 4.19, OH; and 4.49 mu(B), Cl at 295 K, in MeOH) and in the metal-to-ligand charge-transfe r band (500-557 nm); when M = Fe and X = H there is a pronounced spin- crossover equilibrium in methanolic solution (mu(exptl) = 1.31-3.45 mu (B) for 213-328 K). A small variation of the magnetic moments when M = Fe and X = OH (mu(exptl) = 3.77-4.73 mu(B) at 220-332 K) might indica te a temperature-variable population of the 5E(g) sublevel or variatio n in hydrogen bonding. The results are compared with quasi-relativisti c quantum-mechanical calculations, and the spin-crossover behaviour of the new ligands, L, with substituents X = CHO, NH2, CN, Me, NO2, OH, CONH2, COCl, SH, F, Cl, Br or I has been estimated. The differences in the calculated heats of formation between the high-and low-spin forms of [FeL2]2+ when plotted against DELTAdelta (= H-1 NMR para increment for substituents X in benzene) show a turning point in the region aro und X = H and in this region spin-crossover behaviour is observed. Out side this region there is very little or no such behaviour and it is t herefore possible to predict the spin-crossover behaviour for other su bstituents X from the DELTAdelta value.