Department of Chemistry, National Taiwan Normal University, Taipei, 116, Taiwan, Republic of China.
Dalton Trans. 2010 Feb 14;39(6):1492-503. doi: 10.1039/b919176c. Epub 2009 Dec 3.
When TeRu(5)(CO)(14) () was treated with 1 equiv. of CuX (X = Cl, Br, I) in THF, mono-CuX-TeRu(5) clusters TeRu(5)(CO)(14)CuX (X = Cl, ; Br, ; I, ) were obtained. Clusters consist of an octahedral TeRu(5) core, in which one triangular Ru(3) plane is capped by a mu(3)-CuX fragment. For CuX (X = Cl, Br), the reaction of complex with 2 equiv. of CuX in THF at room temperature formed Cu(4)X(2)-linked di-TeRu(5) clusters {TeRu(5)(CO)(14)}(2)Cu(4)X(2) (X = Cl, ; Br, ), while the same reaction in MeCN at -35 degrees C produced bis-CuX-TeRu(5) complexes TeRu(5)(CO)(14)(CuX)(2) (X = Cl, ; Br, ). X-Ray analysis showed that displays a TeRu(5) core with two adjacent Ru(3) triangles each capped by a mu(3)-CuBr ligand while has two TeRu(5) cores that are linked by a mu(6)-Cu(4)Br(2) moiety. Clusters and underwent coupling reactions in THF to yield clusters and , and easily transformed to bis-CuX-Te(2)Ru(4) clusters Te(2)Ru(4)(CO)(10)(CuX)(2) (X = Cl, ; X = Br, ) in MeCN. On the other hand, the reaction of with 2 equiv. of CuI in THF directly produced the bis-CuI-Te(2)Ru(4) cluster Te(2)Ru(4)(CO)(10)(CuI)(2) (). The nature, stability, stepwise cluster transformation, and electrochemistry of these CuX-incorporated TeRu(5)- and Te(2)Ru(4)-based complexes are discussed systematically. In particular, the effects of CuX and the metal cores (TeRu(5)vs. Te(2)Ru(4)) on the resultant Te-Ru-Cu clusters are further elucidated by molecular orbital calculations at the B3LYP level of the density functional theory.
当TeRu(5)(CO)(14)与 1 当量的 CuX（X = Cl、Br、I）在 THF 中反应时，得到单核 CuX-TeRu(5)簇TeRu(5)(CO)(14)CuX（X = Cl、；Br、；I、）。这些簇合物由八面体 TeRu(5)核组成，其中一个三角形 Ru(3)平面被一个μ(3)-CuX 片段封端。对于 CuX（X = Cl、Br），在室温下，将配合物与 2 当量的 CuX 在 THF 中反应，形成 Cu(4)X(2)连接的双 TeRu(5)簇合物{TeRu(5)(CO)(14)}(2)Cu(4)X(2)（X = Cl、；Br、），而在 -35°C 的 MeCN 中进行相同的反应则生成双 CuX-TeRu(5)配合物TeRu(5)(CO)(14)(CuX)(2)（X = Cl、；Br、）。X 射线分析表明，呈现出一个具有两个相邻 Ru(3)三角形的 TeRu(5)核，每个三角形都被一个μ(3)-CuBr 配体封端，而具有两个由μ(6)-Cu(4)Br(2)部分连接的 TeRu(5)核。簇合物和在 THF 中发生偶联反应，生成簇合物和，并且容易在 MeCN 中转化为双 CuX-Te(2)Ru(4)簇合物Te(2)Ru(4)(CO)(10)(CuX)(2)（X = Cl、；X = Br、）。另一方面，与 2 当量的 CuI 在 THF 中的反应直接生成双 CuI-Te(2)Ru(4)簇合物Te(2)Ru(4)(CO)(10)(CuI)(2)（）。系统讨论了这些包含 CuX 的 TeRu(5)-和 Te(2)Ru(4)-基配合物的性质、稳定性、逐步簇转化和电化学性质。特别是，通过密度泛函理论的 B3LYP 水平的分子轨道计算，进一步阐明了 CuX 和金属核（TeRu(5)与 Te(2)Ru(4)）对所得 Te-Ru-Cu 簇合物的影响。
