Copper Halide-Bridged Ruthenium Telluride Carbonyl Complexes: Discovery of the Semiconducting Cluster Chain Polymer [lcub][PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2][sdot]THF[rcub][infin]

The rational synthesis, controllable structure, and special properties of supramolecular aggregates and extended networks constructed from soluble discrete units are currently a very active research area. Recently, a number of extended solids have been constructed, primarily on the basis of coordination or organometallic complexes, and a promising new route to cluster-based frameworks by assembling metal cluster units from solution has emerged, 3] because of their sizes, which start at the bottom end of the nanoregime, and their unique physical properties. So far, such approaches, based on metal carbonyl clusters, have remained rare due to the intrinsic electron deficiency of most metal carbonyl clusters and the lack of available synthetic methodologies. Some notable examples, however, have been reported. For example, Scheer et al. used [{CpMo(CO)2}2Abstract: A new series of Te–Ru–Cu carbonyl complexes was prepared by the reaction of K2TeO3 with [Ru3(CO)12] in MeOH followed by treatment with PPh4X (X=Br, Cl) and [Cu ACHTUNGTRENNUNG(MeCN)4]BF4 or CuX (X=Br, Cl) in MeCN. When the reaction mixture of K2TeO3 and [Ru3(CO)12] was first treated with PPh4X followed by the addition of [Cu ACHTUNGTRENNUNG(MeCN)4]BF4, doubly CuX-bridged Te2Ru4-based octahedral clusters [PPh4]2ACHTUNGTRENNUNG[Te2Ru4(CO)10Cu2X2] (X=Br, [PPh4]2[1]; X=Cl, [PPh4]2[2]) were obtained. When the reaction mixture of K2TeO3 and [Ru3(CO)12] was treated with PPh4X (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 PPh4Br or PPh4Cl followed by CuBr produced the doubly CuBr-bridged cluster 1, the addition of PPh4Cl followed by CuCl led to the formation of the Cu4Cl2bridged bis-TeRu5-based octahedral cluster compound [PPh4]2 ACHTUNGTRENNUNG[{TeRu5ACHTUNGTRENNUNG(CO)14}2ACHTUNGTRENNUNG u4Cl2] ([PPh4]2[3]). On the other hand, when the reaction mixture of K2TeO3 and [Ru3 ACHTUNGTRENNUNG(CO)12] was treated with PPh4Br followed by the addition of CuCl, the Cu(Br)CuCl-bridged Te2Ru4-based octahedral cluster chain polymer {[PPh4]2ACHTUNGTRENNUNG(Te2Ru4ACHTUNGTRENNUNG(CO)10-