Shieh Minghuey, Hsu Miao-Hsing, Sheu Wen-Shyan, Jang Li-Fing, Lin Shu-Fen, Chu Yen-Yi, Miu Chia-Yeh, Lai Yun-Wen, Liu Hsiang-Lin, Her Jim Long
Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan, Republic of China.
Chemistry. 2007;13(23):6605-16. doi: 10.1002/chem.200700135.
A new series of Te-Ru-Cu carbonyl complexes was prepared by the reaction of K(2)TeO(3) with [Ru(3)(CO)(12)] in MeOH followed by treatment with PPh(4)X (X=Br, Cl) and [Cu(MeCN)(4)]BF(4) or CuX (X=Br, Cl) in MeCN. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was first treated with PPh(4)X followed by the addition of [Cu(MeCN)(4)]BF(4), doubly CuX-bridged Te(2)Ru(4)-based octahedral clusters PPh(4)[Te(2)Ru(4)(CO)(10)Cu(2)X(2)] (X=Br, PPh(4)[1]; X=Cl, PPh(4)[2]) were obtained. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)X (X=Br, Cl) followed by the addition of CuX (X=Br, Cl), three different types of CuX-bridged Te-Ru carbonyl clusters were obtained. While the addition of PPh(4)Br or PPh(4)Cl followed by CuBr produced the doubly CuBr-bridged cluster 1, the addition of PPh(4)Cl followed by CuCl led to the formation of the Cu(4)Cl(2)-bridged bis-TeRu(5)-based octahedral cluster compound PPh(4)[{TeRu(5)(CO)(14)}(2)Cu(4)Cl(2)] (PPh(4)[3]). On the other hand, when the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)Br followed by the addition of CuCl, the Cu(Br)CuCl-bridged Te(2)Ru(4)-based octahedral cluster chain polymer {PPh(4)(Te(2)Ru(4)(CO)(10)Cu(4)Br(2)Cl(2)).THF}(infinity) ({PPh(4)[4].THF}(infinity)) was produced. The chain polymer {PPh(4)[4].THF}(infinity) is the first ternary Te-Ru-Cu cluster and shows semiconducting behavior with a small energy gap of about 0.37 eV. It can be rationalized as resulting from aggregation of doubly CuX-bridged clusters 1 and 2 with two equivalents of CuCl or CuBr, respectively. The nature of clusters 1-4 and the formation and semiconducting properties of the polymer of 4 were further examined by molecular orbital calculations at the B3LYP level of density functional theory.
通过在甲醇中使K₂TeO₃与[Ru₃(CO)₁₂]反应，随后用PPh₄X（X = Br、Cl）以及在乙腈中用[Cu(MeCN)₄]BF₄或CuX（X = Br、Cl）处理，制备了一系列新的碲 - 钌 - 铜羰基配合物。当K₂TeO₃与[Ru₃(CO)₁₂]的反应混合物首先用PPh₄X处理，随后加入[Cu(MeCN)₄]BF₄时，得到了双CuX桥联的基于Te₂Ru₄的八面体簇[PPh₄]₂[Te₂Ru₄(CO)₁₀Cu₂X₂]（X = Br，[PPh₄]₂[1]；X = Cl，[PPh₄]₂[2]）。当K₂TeO₃与[Ru₃(CO)₁₂]的反应混合物用PPh₄X（X = Br、Cl）处理，随后加入CuX（X = Br、Cl）时，得到了三种不同类型的CuX桥联的碲 - 钌羰基簇。当加入PPh₄Br或PPh₄Cl随后加入CuBr时，生成了双CuBr桥联的簇1，而加入PPh₄Cl随后加入CuCl则导致形成了Cu₄Cl₂桥联的双TeRu₅基八面体簇化合物[PPh₄]₂[{TeRu₅(CO)₁₄}₂Cu₄Cl₂]（[PPh₄]₂[3]）。另一方面，当K₂TeO₃与[Ru₃(CO)₁₂]的反应混合物用PPh₄Br处理，随后加入CuCl时，则生成了Cu(Br)CuCl桥联的基于Te₂Ru₄的八面体簇链聚合物{[PPh₄]₂(Te₂Ru₄(CO)₁₀Cu₄Br₂Cl₂).THF}∞（{[PPh₄]₂[4].THF}∞）。链聚合物{[PPh₄]₂[4].THF}∞是首个三元碲 - 钌 - 铜簇，表现出半导体行为，其能隙约为0.37 eV。可以合理地认为它是由双CuX桥联的簇1和2分别与两当量的CuCl或CuBr聚集而成。通过密度泛函理论的B3LYP水平的分子轨道计算，进一步研究了簇1 - 4的性质以及聚合物4的形成和半导体性质。
