大环配体过渡金属配合物 Ⅳ.羟基-氧钼(Ⅴ)-(5,10,15,20-四-4-磺酸苯基卟啉)配合物的合成及其性质

TRANSITION METAL COORDINATION COMPOUNDS OF MACROCYCLIC LIGAND Ⅳ. Studies on syntheses and properties of hydroxooxo(5, 10, 15, 20-tetra-4-sulfonato-phenylporphinato molybdenum(Ⅴ)

以Mo(CO)_■和TPPS为原料,在DME溶剂中合成羟基—氧钼(Ⅴ)—(5,10,15,20-四-4-磺酸苯基卟啉)配合物(Mo(Ⅴ)O(OH)TPPS)。对配合物进行紫外可见光谱、电子自旋共振谱和激光拉曼光谱的表征,并用HMO法计算配合物主配体共轭体系Ⅱ分子轨道能级和对称性。由电子自旋共振谱,紫外可见光谱和HMO法计算,推测配合物在酸性水溶液中为C_(4■)对称性的单体Mo(Ⅴ)O(OH)TPPS,而在碱性水榕液中则是D_(2h)点群的二聚体[Mo(Ⅴ)O(OH)TPPS]_2,但是它的一半仍被视为C_(4■)对称性。而在中性水溶液中两者共存。

The hydroxooxo(5, 10, 15, 20-tetra-4-sulfonatophenylporphinato) Molybdenum(V)(Mo(V)O(OH)TPPS)coordination compound was prepared from the corresponding porphyrin with molybdenum hexacarbony1 in DMF. The Product was characterized by UV、ESR and Raman Spectra. Thc Π molecular orbital energy levels was calcalated by HMO method. Both the experiments and HMO Calculation show that the coordination compound exists in a few different forms in aqueous solution with different PH values The coordination compound is in mourner Mo(V)O(OH)TPPS with C_4, Symmetry in acidic aqueous solution The Coordination compouna is in dimer[Mo(V)O(OH)TPPS]_2 wibh D_(2A) symmetry in basic aqueous solution. But there is a monomer-dimer equilibriun accompanied by change of PH values. 2Mo(V)O(OH)TPPS■[Mo(V)O(OH(TPPS]_2