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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The coordination chemistry of selenophosphite ligands. Synthesis and characterization of heterometallic tetranuclear clusters [M{CpFe(CO)2P(Se)(OR)2}3](PF6) (M = Cu, Ag; R = ~nPr, ~iPr) and [Cu(μ-X) {CpFe(CO)2P(Se)(O~iPr)2}]2 (X = Cl, Br)
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The coordination chemistry of selenophosphite ligands. Synthesis and characterization of heterometallic tetranuclear clusters [M{CpFe(CO)2P(Se)(OR)2}3](PF6) (M = Cu, Ag; R = ~nPr, ~iPr) and [Cu(μ-X) {CpFe(CO)2P(Se)(O~iPr)2}]2 (X = Cl, Br)

机译：亚硒酸酯配体的配位化学。杂金属四核簇[M {CpFe（CO）2P（Se）（OR）2} 3]（PF6）（M = Cu，Ag; R =〜nPr，〜iPr）和[Cu（μ-X ）{CpFe（CO）2P（Se）（O〜iPr）2}] 2（X = Cl，Br）

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A neutral selenium donor ligand, [CpFe(CO)2P(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)2P(Se)(OR)2}3](PF6), (where M = Cu, R = ~nPr, 1; R = ~iPr, 2 and M = Ag, R = ~nPr, 3; R = ~iPr, 4) are isolated from the reaction of [M(CH3CN)4(PF6)] (where M = Cu or Ag) and [CpFe(CO)2P(Se)(OR)2] in a molar ratio of 1: 3 in acetonitrile at 0 °C. The reaction of [CpFe(CO)2P(Se)(O~iPr)2] with cuprous halides in acetone produce two mixed-metal, Cu~I_2Fe~(II)_2 clusters, [Cu(μ-X) {CpFe(CO)2P(Se)(O~iPr)2}]2 (X = Cl, 5; Br, 6). All six clusters have been fully characterized spectroscopically (~1H, ~(13)C, ~(31)P, and ~(77)Se NMR, IR), and by elemental analyses. X-Ray crystal structures of 1 and 3 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 1 and 3 crystallize in the noncentrosymmetric, hexagonal space group P62c. 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 5 and 6 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 Cu2X2 parallelogram core. The dihedral angle between the Cu2X2 plane and the plane composed of Cp ring is found to be 24.62 and 84.58° for compound 5 and 6, respectively. Hence the faces of two opposite Cp rings are oriented almost perpendicular to the Cu2X2 plane in 6, but are close to be parallel in 5. This is the first report of the coordination chemistry of the anionic selenophosphito moiety [(RO)2PSe]~-, 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.
机译：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。四个簇[M {CpFe（CO）2P（Se）（OR）2} 3]（PF6），（其中M = Cu，R =〜nPr，1; R =〜iPr，2和M = Ag，R = 〜nPr，3; R =〜iPr，4）从[M（CH3CN）4（PF6）]（其中M = Cu或Ag）和[CpFe（CO）2P（Se）（OR）2在0°C下乙腈中摩尔比为1：3。 [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Cu〜I_2Fe〜（II）_2簇，[Cu（μ-X）{CpFe（ CO）2 P（Se）（O〜iPr）2}] 2（X ＝ Cl，5; Br，6）。所有六个簇均已通过光谱法（〜1H，〜（13）C，〜（31）P和〜（77）Se NMR，IR）进行了充分表征，并已通过元素分析进行​​了表征。 1和3的X射线晶体结构由离散的阳离子簇组成，其中三个铁硒代磷酸酯片段通过硒原子连接至中心铜或银原子。簇1和3都在非中心对称的六边形空间群P62c中结晶。铜或银原子周围的配位几何形状是完美的三角平面，Cu-Se和Ag-Se的距离分别为2.3505（7）和2.5581（7）A。 X射线晶体学还显示，中性杂金属簇5和6中的每个铜中心都与两个卤离子和硒代铁基铁原子中的硒原子呈三角形配位。也可以将结构描述为由反演中心生成的二聚体单元，该单元具有Cu2X2平行四边形核。对于化合物5和6，发现Cu 2 X 2平面和由Cp环组成的平面之间的二面角分别为24.62°和84.58°。因此，两个相对的Cp环的面在6中几乎垂直于Cu2X2平面取向，但在5中接近平行。这是阴离子硒代磷酸部分[（RO）2PSe]〜-的配位化学的首次报道。 ，是次膦硒化物的共轭碱，它作为桥联配体，在铁上具有P配位，在Se上与铜或银配位。

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