Interconversion between ladder-type octanuclear and linear tetranuclear copper(I) complexes supported by tetraphosphine ligands.
Interconversion between ladder-type octanuclear and linear tetranuclear copper(I) complexes supported by tetraphosphine ligands.
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DOI：
10.1039/b909252h
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发表时间：
2009-11
影响因子：
4
通讯作者：
Y. Takemura;Takayuki Nakajima;T. Tanase
中科院分区：
文献类型：
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作者：
Y. Takemura;Takayuki Nakajima;T. Tanase
线性有序四膦，内消旋双[(二苯基膦甲基)苯基膦]甲烷(dpmppm)，很容易与4当量反应。 CuX在二氯甲烷中生成八核铜(I)配合物，[Cu(8)(mu-X)(8)(mu-dpmppm)(2)] (X = Cl (1a), Br (1b), I (1c))，其涉及由两个反排列的 dpmppm 配体支撑的梯型 {Cu(8)(mu-X)(2)(mu(3)-X)(6)} 核。通过用 Cu(OTf)(2) 处理，将复合物 1a 进一步转化为 [Cu(8)(mu-X)(6)(OTf)(2)(mu-dpmppm)(2)] (2)，其中两个 TfO 阴离子附着在 Cu(8) 阶梯的两端。当配合物 1 在 2 当量存在下溶解在二甲基亚砜 (dmso) 中时。 dpmppm 后，八铜 (I) 梯子被解开，得到线性四核铜 (I) 络合物 [Cu(4)X(mu-X)(3)(mu-dpmppm)(2)(dmso)] (X = Cl (3a)、Br (3b)、I (3c))。用 2 当量的 dpmppm 进行类似处理。 CuX 在配位溶剂 N,N'-二甲基甲酰胺 (dmf) 和吡啶 (py) 存在下生成对称的四铜 (I) 配合物 [Cu(4)(mu-Cl)(3)(mu-dpmppm)(2)(dmf)(2)][CuCl(2)] (4) 和[Cu(4)(mu-I)(3)(mu-dpmppm)(2)(py)(2)]I (5)。获得了一系列带有末端异氰化物配体的四铜(I)络合物，[Cu(4)(mu-X)(3)(mu-dpmppm)(2)(RNC)(2)]PF(6) (X = Cl, R = Xyl (6a); X = Br, R = Mes (7b); X = I, R = Xyl (8a), Mes (8b), (t)Bu (8c))来自 dpmppm 与 2 当量的反应。 CuX 在 dmf 或乙腈中，然后添加过量的 RNC 和 NH(4)PF(6)。配合物 3-8 具有弯曲的 Cu(4)(mu-X)(3) 链，由顺式排列的两个 dpmppm 配体支撑，其中末端位点具有反应性并可容纳各种末端配体。当配合物8c在CH(3)CN-CH(2)Cl(2)混合溶剂中用AgPF(6)处理时，软路易斯酸性Ag(I)离子将铜(I)结合dpmppm脱落，所得两个{Cu(4)(mu-I)(3)(mu-dpmppm)((t)BuNC)(2)}(+)片段被拉上拉链，形成梯型八铜(I)配合物， [Cu(8)(mu-I)(6)(mu-dpmppm)(2)((t)BuNC)(2)](PF(6))(2) (9)。 Cu(8)梯和Cu(4)链之间的明显相互转化可能通过具有{Cu(4)(mu-X)(3)(mu-dpmppm)}(+)单元的不稳定中间体进行，这可能是进一步延伸的卤化铜(I)簇的有用合成子。
Linearly ordered tetraphosphine, meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm), readily reacted with 4 equiv. of CuX in dichloromethane to afford octanuclear copper(I) complexes, [Cu(8)(mu-X)(8)(mu-dpmppm)(2)] (X = Cl (1a), Br (1b), I (1c)), which involve a ladder-type {Cu(8)(mu-X)(2)(mu(3)-X)(6)} core supported by two dpmppm ligands in anti arrangement. Complex 1a was further transformed by treatment with Cu(OTf)(2) into [Cu(8)(mu-X)(6)(OTf)(2)(mu-dpmppm)(2)] (2) in which two TfO anions attached to both end of the Cu(8) ladder. When complexes 1 were dissolved in dimethyl sulfoxide (dmso) in the presence of 2 equiv. of dpmppm, the octacopper(I) ladder was unzipped to result in the linear tetranuclear copper(I) complex, [Cu(4)X(mu-X)(3)(mu-dpmppm)(2)(dmso)] (X = Cl (3a), Br (3b), I (3c)). Similar treatment of dpmppm with 2 equiv. of CuX in the presence of coordinative solvents, N,N'-dimethylformamide (dmf) and pyridine (py), yielded the symmetrical tetracopper(I) complexes, [Cu(4)(mu-Cl)(3)(mu-dpmppm)(2)(dmf)(2)][CuCl(2)] (4) and [Cu(4)(mu-I)(3)(mu-dpmppm)(2)(py)(2)]I (5). A series of tetracopper(I) complexes with terminal isocyanide ligands, [Cu(4)(mu-X)(3)(mu-dpmppm)(2)(RNC)(2)]PF(6) (X = Cl, R = Xyl (6a); X = Br, R = Mes (7b); X = I, R = Xyl (8a), Mes (8b), (t)Bu (8c)), were obtained from reactions of dpmppm with 2 equiv. of CuX in dmf or acetonitrile followed by addition of an excess of RNC and NH(4)PF(6). Complexes 3-8 possess a bending Cu(4)(mu-X)(3) chain supported by two dpmppm ligands in syn arrangement, where the terminal sites are reactive and accommodate a variety of terminal ligands. When complex 8c was treated with AgPF(6) in a CH(3)CN-CH(2)Cl(2) mixed solvent, the soft Lewis acidic Ag(I) ions took the copper(I)-binding dpmppm off and the resultant two {Cu(4)(mu-I)(3)(mu-dpmppm)((t)BuNC)(2)}(+) fragments were zipped up to form the ladder-type octacopper(I) complex, [Cu(8)(mu-I)(6)(mu-dpmppm)(2)((t)BuNC)(2)](PF(6))(2) (9). The apparent interconversion between the Cu(8) ladder and the Cu(4) chain might proceed through a labile intermediate with a {Cu(4)(mu-X)(3)(mu-dpmppm)}(+) unit, which could be useful synthon of further extended copper(I) halide clusters.