四(亚硝基)合钯酸钾的合成、单晶结构及其循环伏安特征

Synthesis,single-crystal structure and cyclic voltammetry of potassium tetranitropalladate(II)

以醋酸钯(PdAc_(2))与亚硝酸钾(KNO_(2))为起始原料,水为溶剂,合成四亚硝基钯酸钾(K_(2)[Pd(NO_(2))_(4)]),产率为96.5%。采用溶剂挥发法培养出其单晶,经X射线单晶衍射分析证实:此晶体由中心对称的[Pd(NO_(2))_(4)]^(2-)配阴离子,K+阳离子和2分子结晶水组成,为三斜晶系,P-1空间群,晶胞参数为:a=6.4953(5)nm,b=7.0134(5)nm,c=7.1473(5)nm,α=118.784(2)°,β=101.050(2)°,γ=98.085(2)°,Z=1,Pd-N键长为2.014 nm和2.037 nm,∠N-Pd-N为91.70(4)°,且Pd^(2+)位于4个N原子组成的平面四边形的中心。采用恒电位仪在室温下测试其循环伏安图,测得其还原峰电位(Ep)为-0.51 V(vs.SCE)。

Potassium tetranitropalladate(II)was synthesized in one step by mixing palladium acetate and potassium nitrite in water with a yield of 96.5%.A single crystal of the product was cultivated using a solvent evaporation method,and was characterized by X-ray single crystal diffraction analysis.The crystal unit of the compound contains one centrosymmetric[Pd(NO_(2))_(4)]^(2)-complex anion,two K+cations and two crystallized water molecules,belongs to triclinic crystal system and P-1 space group.The unit cell parameters are a=6.4953(5)nm,b=7.0134(5)nm,c=7.1473(5)nm,α=118.784(2)°,β=101.050(2)°,γ=98.085(2)°,Z=1.The Pd-N bond lengths are 2.014 and 2.037 nm,∠N-Pd-N is 91.70(4)°,revealing that Pd^(2+)is in the center of the planar quadrilateral formed by four N atoms from the nitro groups.The cyclic voltammetry was measured at room temperature,and the reduction peak potential(Ep)was found to be-0.51 V(vs.SCE).