论文部分内容阅读
合成了2个新的单核双氧基钼(Ⅵ)配合物,其分子式通式为[Mo O2L(Me OH)],其中L1和L2分别是N′-(3-溴-2-羟基苯亚甲基)-3,5-二甲氧基苯甲酰肼和N′-(5-溴-2-羟基苯亚甲基)异烟肼的二价阴离子,通过理化手段、光谱方法以及单晶X射线衍射表征了它们的结构。配合物1以单斜晶系P21/n空间群结晶,其晶体学参数a=0.848 98(3)nm,b=2.275 4(1)nm,c=1.069 82(5)nm,β=109.108(1)°,V=1.952 8(1)nm3,Z=4,R1=0.036 7,w R2=0.084 0,S=1.027。配合物2以三斜晶系P1空间群结晶,其晶体学参数a=0.655 05(9)nm,b=1.076 63(7)nm,c=1.303 3(1)nm,α=67.383(2)°,β=84.264(1)°,γ=76.195(2)°,V=0.823 9(1)nm3,Z=2,R1=0.071 3,w R2=0.151 0,S=1.004。X射线分析表明2个配合物中的Mo原子都采取八面体配位构型,配位原子分别来自酰腙配体的NO2给体基团和甲醇氧原子。催化实验表明2个配合物都是有效的烯烃氧化催化剂。
Two novel mononuclear dioxo molybdenum (VI) complexes were synthesized and the general formula is [Mo O2L (Me OH)], where L1 and L2 are N ’- (3-bromo- Methylene) -3,5-dimethoxybenzohydrazide and N ’- (5-bromo-2-hydroxybenzylidene) isoniazid by the physicochemical means, spectroscopic methods and single Crystal X-ray diffraction characterizes their structure. The complex 1 crystallizes in the monoclinic P21 / n space group and its crystallographic parameters a = 0.848 98 (3) nm, b = 2.275 4 (1) nm, c = 1.069 82 (5) nm and β = 109.108 1) °, V = 1.952 8 (1) nm3, Z = 4, R1 = 0.036 7, w R2 = 0.084 0, S = 1.027. The complex 2 crystallizes in the triclinic P1 space group and its crystallographic parameters a = 0.655 05 (9) nm, b = 1.076 63 (7) nm, c = 1.303 3 °, β = 84.264 (1) °, γ = 76.195 (2) °, V = 0.823 9 (1) nm3, Z = 2, R1 = 0.071 3, w R2 = 0.151 0, S = 1.004. X-ray analysis showed that the Mo atoms in the two complexes all adopt the octahedral coordination structure, and the coordination atoms are derived from the NO2 donor group and the methanol oxygen atom of the acylhydrazone ligand, respectively. Catalytic experiments show that both complexes are effective olefin oxidation catalysts.