Bimetallic Ru–Cu tellurido complexes: controlled synthesis and electrochemical studies of copper halide–TeRu5 and Te2Ru4clusters
作者:Minghuey Shieh、Yen-Yi Chu、Chia-Yeh Miu、Pei-Fan Wu、Tsau-Ming Zeng
DOI:10.1039/b919176c
日期:——
When [TeRu5(CO)14]2â (1) was treated with 1 equiv. of CuX (X = Cl, Br, I) in THF, mono-CuXâTeRu5 clusters [TeRu5(CO)14CuX]2â (X = Cl, 2a; Br, 2b; I, 2c) were obtained. Clusters 2aâ2c consist of an octahedral TeRu5 core, in which one triangular Ru3 plane is capped by a μ3-CuX fragment. For CuX (X = Cl, Br), the reaction of complex 1 with 2 equiv. of CuX in THF at room temperature formed Cu4X2-linked di-TeRu5 clusters [TeRu5(CO)14}2Cu4X2]2â (X = Cl, 3a; Br, 3b), while the same reaction in MeCN at â35 °C produced bis-CuXâTeRu5 complexes [TeRu5(CO)14(CuX)2]2â (X = Cl, 4a; Br, 4b). X-Ray analysis showed that 4b displays a TeRu5 core with two adjacent Ru3 triangles each capped by a μ3-CuBr ligand while 3b has two TeRu5 cores that are linked by a μ6-Cu4Br2 moiety. Clusters 4a and 4b underwent coupling reactions in THF to yield clusters 3a and 3b, and easily transformed to bis-CuXâTe2Ru4 clusters [Te2Ru4(CO)10(CuX)2]2â (X = Cl, 5a; X = Br, 5b) in MeCN. On the other hand, the reaction of 1 with 2 equiv. of CuI in THF directly produced the bis-CuIâTe2Ru4 cluster [Te2Ru4(CO)10(CuI)2]2â (5c). The nature, stability, stepwise cluster transformation, and electrochemistry of these CuX-incorporated TeRu5- and Te2Ru4-based complexes are discussed systematically. In particular, the effects of CuX and the metal cores (TeRu5vs. Te2Ru4) on the resultant TeâRuâCu clusters are further elucidated by molecular orbital calculations at the B3LYP level of the density functional theory.
将[TeRu5(CO)14]2â (1)与 1 等量的 CuX(X = Cl、Br、I)在四氢呋喃中进行处理,可得到单-CuX-TeRu5 簇[TeRu5(CO)14CuX]2â(X = Cl,2a;Br,2b;I,2c)。簇 2aâ2c 由一个八面体 TeRu5 核心组成,其中一个三角形 Ru3 平面被一个 μ3-CuX 片段覆盖。对于 CuX(X = Cl、Br),复合物 1 与 2 等量的 CuX 在四氢呋喃(THF)中发生反应,反应温度为 20°C 至 50°C。对于 CuX(X = Cl、Br),络合物 1 与 2 等价的 CuX 在 THF 中于室温反应生成 Cu4X2 链接的二 TeRu5 簇合物 [TeRu5(CO)14}2Cu4X2]2â (X = Cl,3a;Br,3b),而在 MeCN 中于 §35 °C 进行相同反应则生成双 CuXâTeRu5 络合物 [TeRu5(CO)14(CuX)2]2â (X = Cl,4a;Br,4b)。X 射线分析表明,4b 显示了一个 TeRu5 核心和两个相邻的 Ru3 三角形,每个三角形都被δ3-CuBr 配体封盖;而 3b 则显示了两个 TeRu5 核心,它们通过一个δ6-Cu4Br2 分子相连。簇 4a 和 4b 在四氢呋喃中发生偶联反应,生成簇 3a 和 3b,并在 MeCN 中很容易转化为双 CuXâTe2Ru4 簇 [Te2Ru4(CO)10(CuX)2]2â (X = Cl,5a;X = Br,5b)。另一方面,1 与 2 等量的 CuI 在 THF 中反应,直接生成了双 CuIâTe2Ru4 簇[Te2Ru4(CO)10(CuI)2]2â(5c)。本文系统地讨论了这些 CuX 嵌入的 TeRu5- 和 Te2Ru4 基配合物的性质、稳定性、逐步簇转变和电化学特性。特别是通过密度泛函理论 B3LYP 水平的分子轨道计算,进一步阐明了 CuX 和金属内核(TeRu5 与 Te2Ru4)对生成的 TeâRuâCu 簇的影响。