Synthesis and Characterization of Linear Tetra nuclear Silver(I) Complexes Bridged by Tetraphosphine Ligands
Synthesis and Characterization of Linear Tetra nuclear Silver(I) Complexes Bridged by Tetraphosphine Ligands
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四膦配体桥接的线性四核银(I)配合物的合成与表征
DOI：
10.1002/ejic.200900652
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发表时间：
2009
期刊：
影响因子：
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通讯作者：
and T. Tanase
中科院分区：
文献类型：
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作者：
Y. Takemura;T. Nakajima;and T. Tanase
AgOTf withmeso‐bis[(diphenylphosphanylmethyl)phenylphosphanyl]methane(Dpmppm)afforded[Ag4(OTf)2(μ‐OTf)(μ‐dpmppm)2{(CH3)2CO}](OTf)(1)与[Ag4(OTf)2(μ-OTf)(μ-dpmppm)2(Rnc)2](OTf){R=XYL(2a)，MES(2b)，TbU(2c)的反应。当AgOTf在空气中与dpmppm反应时，C-Cl和P-C键发生断裂，生成[Ag4(μ-Cl)(μ-dpmppm)2(TBuNC)4](OTf)3(3)和[Ag4(μ-Ph2PO2)(μ-dpmppm)2(TBuNC)3](OTf)3(4)。AgOCOCF3与dpmppm反应生成[Ag4(OCOCF3)2(μ-OCOCF3)(μ-dpmppm)2](CF3COO)(5)。用dpmppm与AgPF6反应，得到了[Ag4(μ-dpmppm)2(TBuNC)4](PF6)4(6)和[Ag4(PO2F2)2(μ-dpmppm)2(TBuNC)2](PF6)2(7)。络合物1-3具有一个{Ag4(μ-dpmppm)2}4+核，其中Ag4弦与两个dpmppm配体以非同步方式排列而相当弯曲，络合物4-7具有由两个dpmppm配体以反方式排列支撑的线形Ag4弦。这些结果表明，dpmppm支撑的四银(I)弦是相当灵活和不稳定的，因此作为多金属中心的结果，在促进有机反应方面具有潜在的重要作用。
Reactions of AgOTf withmeso‐bis[(diphenylphosphanylmethyl)phenylphosphanyl]methane (dpmppm) afforded[Ag4(OTf)2(μ‐OTf)(μ‐dpmppm)2{(CH3)2CO}](OTf) (1) and [Ag4(OTf)2(μ‐OTf)(μ‐dpmppm)2(RNC)2](OTf) {R = Xyl (2a), Mes (2b),tBu (2c)}. When AgOTf was treated with dpmppm in air in the presence oftBuNC, cleavage of the C–Cl and P–C bonds occurred to give [Ag4(μ‐Cl)(μ‐dpmppm)2(tBuNC)4](OTf)3(3) and [Ag4(μ‐Ph2PO2)(μ‐dpmppm)2(tBuNC)3](OTf)3(4). Reaction of AgOCOCF3with dpmppm resulted in [Ag4(OCOCF3)2(μ‐OCOCF3)(μ‐dpmppm)2](CF3COO) (5). By treatment of AgPF6with dpmppm, [Ag4(μ‐dpmppm)2(tBuNC)4](PF6)4(6) and [Ag4(PO2F2)2(μ‐dpmppm)2(tBuNC)2] (PF6)2(7) were obtained. Wheareas complexes1–3possess a {Ag4(μ‐dpmppm)2}4+core in which the Ag4strings are rather bent with two dpmppm ligands arranged in asynfashion, complexes4–7have linear Ag4strings supported by two dpmppm ligands arranged in anantifashion. These results suggest that the dpmppm‐supported tetrasilver(I) strings are quite flexible and labile and thus are potentially important in promoting organic reactions as a result of the multimetallic centers.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)