Bimetallic Ru-Cu tellurido complexes: controlled synthesis and electrochemical studies of copper halide-TeRu(5) and Te(2)Ru(4) clusters.
When [TeRu(5)(CO)(14)](2-) () was treated with 1 equiv. of CuX (X = Cl, Br, I) in THF, mono-CuX-TeRu(5) clusters [TeRu(5)(CO)(14)CuX](2-) (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)](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)](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)](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)](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.
Shieh
Minghuey
M
Department of Chemistry, National Taiwan Normal University, Taipei, 116, Taiwan, Republic of China. mshieh@ntnu.edu.tw
Chu
Yen-Yi
YY
Miu
Chia-Yeh
CY
Wu
Pei-Fan
PF
Zeng
Tsau-Ming
TM