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Copper Halide‐Bridged Ruthenium Telluride Carbonyl Complexes: Discovery of the Semiconducting Cluster Chain Polymer {[PPh 4 ] 2 [Te 2 Ru 4 (CO) 10 Cu 4 Br 2 Cl 2 ]⋅THF} ∞

2007; Wiley; Volume: 13; Issue: 23 Linguagem: Inglês

10.1002/chem.200700135

1521-3765

Minghuey Shieh, Miao‐Hsing Hsu, Wen‐Shyan Sheu, Li‐Fing Jang, Shu-Fen Lin, Yen‐Yi Chu, Chia‐Yeh Miu, Yun‐Wen Lai, Hsiang‐Lin Liu, Jim-Long Her,

Metalloenzymes and iron-sulfur proteins

Abstract 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 ] 2 [Te 2 Ru 4 (CO) 10 Cu 2 X 2 ] (X=Br, [PPh 4 ] 2 [ 1 ]; X=Cl, [PPh 4 ] 2 [ 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 ] 2 [{TeRu 5 (CO) 14 } 2 Cu 4 Cl 2 ] ([PPh 4 ] 2 [ 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 ] 2 (Te 2 Ru 4 (CO) 10 Cu 4 Br 2 Cl 2 )⋅THF} ∞ ({[PPh 4 ] 2 [ 4 ]⋅THF} ∞ ) was produced. The chain polymer {[PPh 4 ] 2 [ 4 ]⋅THF} ∞ 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.