两个异亚硝基乙酰丙酮-N-芳基亚胺Pd(Ⅱ)配合物的合成、谱学性质和PdCl(C_6H_5—IAI)(C_6H_5NH_2)的晶体结构

Syntheses and Spectral Properties of Two Complexes of Isonitrosoacetylacetone- N -arylimine and Crystal Structure of PdCl(C_6H_5-IAI)(C_6H_5NH_2)

合成了两个异亚硝基乙酰丙酮 N 芳基亚胺的Pd(Ⅱ )配合物 ,PdCl(C6H5—IAI) (C6H5NH2 ) ( 1 )和PdCl( p CH3 C6H4 —IAI) ( p CH3 C6H4 NH2 ) ( 2 ) ,并测定了配合物 1的晶体结构 .配合物 1晶体属正交晶系 ,空间群为Pca2 1,晶胞参数a =1 .8587( 4 )nm ,b=0 .93 80 ( 2 )nm ,c=2 .1 2 3 7( 4 )nm ,Z =8,F( 0 0 0 ) =1760 ,μ =1 .1 60mm-1,R1=0 .0 2 71 .二齿Schiff碱配体的异亚硝基 (肟基 )的N原子和亚胺的N原子 ,苯胺基N原子和Cl-离子与Pd(Ⅱ )配位 ,形成PdN3 Cl平面正方形配位构型 .红外和喇曼光谱表明 ,形成配合物后νCO和νCN移向低频 ,而νN—O则移向高频 .电子光谱说明存在π π 和d π

Two complexes of isonitrosoacetylacetone N arylimine, PdCl(C 6H 5\_IAI)(C 6H 5NH 2)(1) and PdCl( p CH 3C 6H 4\_IAI)( p CH 3C 6H 4NH 2)(2), were synthesized and characterized by IR and Raman spectroscopy. Complex 1 crystallizes in orthorhombic system, space group Pca 2 1, with parameters a =1.858 7(4) nm, b =0.938 0(2) nm, c =2.123 7(4) nm, V =3.702(1) nm 3, D c=1.572 g/cm 3, Z =8, F (000)=1 760 , μ =1.160 mm -1 . The final R 1 value is 0.027 1 for 3 592 observed reflections with \{I≥2σ(I)\} . The Pd(Ⅱ) ion has a distorted square planar PdN 3Cl coordination composed of imino nitrogen and oximo nitrogen from the Schiff base ligand, amino nitrogen from aniline and chlorine anion. The oxime group of the Schiff base ligand is coordinated to the Pd(Ⅱ) through its oximo nitrogen atom, but not its oximo oxygen atom. The ν CO and ν CN bands display a shift to lower frequencies and ν N O bands to higher frequencies in IR and Raman spectra. There are π π * transition and d π * charge transfer transition in electronic spectra. [WT5HZ]