Synthesis and characterization of 8-quinolinolato vanadium(IV) complexes

摘要

Reaction of vanadium(III) chloride with 8-quinolinol (Hqn) gave a mononuclear vanadium(IV) complex, [VOC1_2(H_20)_2] 1) _ 2H_2qn _ 2Cl _ CH_3CN, and three dinuclear vanadium(IV) complexes: [V_20_2C1_2 (qn)_2(H_20)_2] (2). Hqn, [V_20_2C1_2(qn)_2(C_3H_7OH)_2] (3), and [V_20_2C1_2(qn)_2(C_4H_9OH)_2] (4). Reaction of vana_dium(III) chloride with 5-chloro-8-quinolinol (HClqn) gave four dinuclear vanadium(IV) complexes: [V_20_2C1_2(Clqn)_2(H_20)_2] (5) 2HCIqn, [V_20_2C1_2(Clqn)_2(C_3H_7OH)_2] (6), [V_20_2C1_2(Clqn)_2(C_6H_5CH_2OH)_2] (7), and [V_20_2C12(Clqn)_2(C_4H_9OH)_2] (8) . 2C_4H_9OH.Rgaction of vanadium(III) chloride with 5-fluoro-8-quino_linol (HFqn) gave two dinuclear vanadium(IV) complexes: [V_20_2C1_2(Fqn)_2(H_20)_2] (9) HFqn _ 2H_20 and V_20_2C1_2(Fqn)_2(C_3H_7OH)_2] (10). X-ray structures of 1 _ 2H_2qn _ 2Cl _ CH_3CN, 3, 4, 6, 7, 8 2 t-BuOH, and 10 have been determined. As to the mononuclear species 1 2H_2qn - 2C1 _ CH_3CN, coordination of Hqn to vanadium does not occur, but protonation to Hqn occurs to give H_2gn~+, which links l's through hydrogen bonding, while each of the dinuclear species has a terminal and a bridging qn (or Clgn, Fqn) ligand, giving rise to a (V-0)_2 ring. Magnetic measurements of 3, 4, 6, 7, and 10 in solid form show very weak antiferromagnetic behavior, and the effective magnetic moments are close to spin only value (2.44) of d'-d' system, while ESR of 3 in THE shows dissociation to monomeric species. Change from mononuclear, 1, to dinuclear, 2, species was followed by the change of electronic spectrum.