Shieh Minghuey, Miu Chia-Yeh, Hsing Kai-Jieah, Jang Li-Fing, Lin Chien-Nan
Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan, Republic of China.
Dalton Trans. 2015 Apr 14;44(14):6526-36. doi: 10.1039/c5dt00546a.
Two sandwich-type Cu3Cl- or Cu2{Te2Ru4(CO)10}-bridging di-TeRu5 clusters, {TeRu5(CO)14}2Cu3Cl () and {TeRu5(CO)14}2Cu2{Te2Ru4(CO)10} (), were obtained from the reaction of TeRu5(CO)14 with 1 equiv. of [Cu(MeCN)4][BF4] in CH2Cl2 or THF at 0 °C, respectively, depending on the solvents. The chloride-abstracted was structurally characterized to have two TeRu5 cores that were linked by a Cu3Cl moiety with two Cu-Cu bonds. If the reaction was carried out in a molar ratio of 1 : 2 at 0 or 30 °C in CH2Cl2, the structural isomers [TeRu5(μ-CO)2(CO)12(CuMeCN)2] () and [TeRu5(μ-CO)3(CO)11Cu2(MeCN)2] () were produced, respectively, as the major product. Cluster displayed a TeRu5 core with two adjacent Ru3 triangles each capped by a μ3-Cu(MeCN) fragment, while contained a TeRu5 core with one triangle Ru3 plane capped by a Cu2(MeCN)2 fragment with two Cu atoms covalently bonded. Upon heating, the isomerization of into proceeded to undergo an unusual skeletal arrangement of Cu(MeCN) and migration of CO, with the TeRu5 core remaining intact. An electrochemical study revealed that and each exhibited only one oxidation while cluster had two consecutive oxidations, suggesting significant electronic communication between the two TeRu5 metal cores in via the Cu3 moiety. This work describes the facile synthesis of a series of semiconducting Cux-bridging Te-Ru carbonyl clusters, in which the incorporation of the Cux fragments has significantly influenced their resulting structures, rearrangements, and electronic properties, which was further elucidated by DFT calculations.
通过将TeRu5(CO)14与1当量的[Cu(MeCN)4][BF4]分别在二氯甲烷或四氢呋喃中于0°C反应，根据溶剂的不同，得到了两个三明治型的由Cu3Cl或Cu2{Te2Ru4(CO)10}桥连的双碲钌簇，即{TeRu5(CO)14}2Cu3Cl( )和{TeRu5(CO)14}2Cu2{Te2Ru4(CO)10}( )。经结构表征，脱氯产物有两个由一个带有两个Cu-Cu键的Cu3Cl部分相连的TeRu5核。如果反应在二氯甲烷中于0或30°C以1∶2的摩尔比进行，则分别生成结构异构体TeRu5(μ-CO)2(CO)12(CuMeCN)2 )和TeRu5(μ-CO)3(CO)11Cu2(MeCN)2作为主要产物。簇合物 显示一个TeRu5核，其中两个相邻的Ru3三角形各由一个μ3-Cu(MeCN)片段封端，而 包含一个TeRu5核，其中一个三角形Ru3平面由一个带有两个共价键合的Cu原子的Cu2(MeCN)2片段封端。加热时， 异构化为 会发生Cu(MeCN)的异常骨架排列和CO的迁移，而TeRu5核保持完整。电化学研究表明， 和 各自仅表现出一次氧化，而簇合物 有两次连续氧化，这表明 中两个TeRu5金属核之间通过Cu3部分存在显著的电子通信。这项工作描述了一系列半导体Cux桥连的碲-钌羰基簇合物的简便合成方法，其中Cux片段的引入显著影响了它们的结构、重排和电子性质，密度泛函理论计算进一步阐明了这一点。
