Santra Bidyut Kumar, Chen Jia-Li, Sarkar Bijay, Liu C W
Department of Chemistry, National Dong Hwa University, Hualien, Taiwan.
Dalton Trans. 2008 May 7(17):2270-6. doi: 10.1039/b717963d. Epub 2008 Feb 28.
A neutral selenium donor ligand, [CpFe(CO)(2)P(Se)(OR)(2)] is used for the construction of Cu(I) and Ag(I) complexes with a well-defined coordination environment. Four clusters M{CpFe(CO)(2)P(Se)(OR)(2)}(3), (where M = Cu, R = (n)Pr, ; R = (i)Pr, and M = Ag, R = (n)Pr, ; R = (i)Pr, ) are isolated from the reaction of [M(CH(3)CN)(4)(PF(6))] (where M = Cu or Ag) and [CpFe(CO)(2)P(Se)(OR)(2)] in a molar ratio of 1 : 3 in acetonitrile at 0 degrees C. The reaction of [CpFe(CO)(2)P(Se)(O(i)Pr)(2)] with cuprous halides in acetone produce two mixed-metal, Cu(I)(2)Fe(II)(2) clusters, Cu(mu-X) {CpFe(CO)(2)P(Se)(O(i)Pr)(2)} (X = Cl, ; Br, ). All six clusters have been fully characterized spectroscopically ((1)H, (13)C, (31)P, and (77)Se NMR, IR), and by elemental analyses. X-Ray crystal structures of and consist of discrete cationic clusters in which three iron-selenophosphito fragments are linked to the central copper or silver atom via selenium atoms. Both clusters and crystallize in the noncentrosymmetric, hexagonal space group P6[combining macron]2c. The coordination geometry around the copper or silver atom is perfect trigonal-planar with Cu-Se and Ag-Se distances, 2.3505(7) and 2.5581(7) A, respectively. X-Ray crystallography also reveals that each copper center in neutral heterometallic clusters and is trigonally coordinated to two halide ions and a selenium atom from the selenophosphito-iron moiety. The structures can also be delineated as a dimeric unit which is generated by an inversion center and has a Cu(2)X(2) parallelogram core. The dihedral angle between the Cu(2)X(2) plane and the plane composed of Cp ring is found to be 24.62 and 84.58 degrees for compound and , respectively. Hence the faces of two opposite Cp rings are oriented almost perpendicular to the Cu(2)X(2) plane in , but are close to be parallel in . This is the first report of the coordination chemistry of the anionic selenophosphito moiety (RO)(2)PSe, the conjugated base of a secondary phosphine selenide, which acts as a bridging ligand with P-coordination on iron and Se-coordination to copper or silver.
一种中性硒供体配体[CpFe(CO)₂P(Se)(OR)₂]用于构建具有明确配位环境的Cu(I)和Ag(I)配合物。从M(CH₃CN)₄（其中M = Cu或Ag）与[CpFe(CO)₂P(Se)(OR)₂]在乙腈中于0℃以1:3的摩尔比反应中分离出四个簇合物M{CpFe(CO)₂P(Se)(OR)₂}₃（其中M = Cu，R = nPr；R = iPr，以及M = Ag，R = nPr；R = iPr）。[CpFe(CO)₂P(Se)(O iPr)₂]与卤化亚铜在丙酮中的反应生成两个混合金属的Cu(I)₂Fe(II)₂簇合物[Cu(μ - X){CpFe(CO)₂P(Se)(O iPr)₂}]₂（X = Cl；Br）。所有六个簇合物均已通过光谱表征（¹H、¹³C、³¹P和⁷⁷Se NMR、IR）以及元素分析进行了全面表征。和的X射线晶体结构由离散的阳离子簇组成，其中三个铁硒磷酰亚胺片段通过硒原子与中心铜或银原子相连。簇合物和均结晶于非中心对称的六方空间群P6₂c。铜或银原子周围的配位几何构型为完美的三角平面，Cu - Se和Ag - Se距离分别为2.3505(7) Å和2.5581(7) Å。X射线晶体学还表明，中性异金属簇合物和中的每个铜中心与两个卤离子以及来自硒磷酰亚胺 - 铁部分的一个硒原子呈三角配位。这些结构也可描述为由一个反演中心产生的二聚体单元，具有Cu₂X₂平行四边形核心。发现化合物和中Cu₂X₂平面与由Cp环组成平面之间的二面角分别为24.62°和84.58°。因此，在中两个相对Cp环的面几乎垂直于Cu₂X₂平面，但在中则接近平行。这是关于阴离子硒磷酰亚胺部分[(RO)₂PSe]⁻配位化学的首次报道，它是仲膦硒化物的共轭碱，作为一种桥连配体，在铁上进行P配位，在铜或银上进行Se配位。
