Abstract
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(MeCN) 4]BF4 or CuX (X = Br, C1) in MeCN. When the reaction mixture of K2TeO3 and [Ru3(CO)12] was first treated with PPh4X followed by the addition of [Cu(MeCN)4]BF4, doubly CuX-bridged Te2Ru 4-based octahedral clusters [PPh4]2[Te 2Ru4(CO)10Cu2X2] (X = Br, [PPh4]2[1]; X = Cl, [PPh4J2P]) 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-TeRu 5-based octahedral cluster compound [PPh4] 2[{TeRu5(CO)14}2Cu 4Cl2] ([PPh4]2[3]). On the other hand, when the reaction mixture of K2TeO3 and [Ru 3(CO)12] was treated with PPh4Br followed by the addition of CuCl, the Cu(Br)CuCl-bridged Te2Ru4-based octahedral cluster chain polymer {[PPh4]2(Te2Ru 4(CO)10-Cu4Br2Cl2)THFL ({[PPh4]2[4]·[THF)∞) was produced. The chain polymer {[PPh4]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.
| Original language | English |
|---|---|
| Pages (from-to) | 6605-6616 |
| Number of pages | 12 |
| Journal | Chemistry - A European Journal |
| Volume | 13 |
| Issue number | 23 |
| DOIs | |
| Publication status | Published - 2007 Aug 14 |
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Keywords
- Carbonyl ligands
- Cluster compounds
- Copper
- Ruthenium
- Tellurium
ASJC Scopus subject areas
- Catalysis
- Organic Chemistry
Cite this
Copper halide-bridged ruthenium telluride carbonyl complexes : Discovery of the semiconducting cluster chain polymer {[PPh4]2[Te 2Ru4(CO)10Cu4Br2Cl 2]·THF∞. / 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.
In: Chemistry - A European Journal, Vol. 13, No. 23, 14.08.2007, p. 6605-6616.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Copper halide-bridged ruthenium telluride carbonyl complexes
T2 - Discovery of the semiconducting cluster chain polymer {[PPh4]2[Te 2Ru4(CO)10Cu4Br2Cl 2]·THF∞
AU - Shieh, Minghuey
AU - Hsu, Miao Hsing
AU - Sheu, Wen Shyan
AU - Jang, Li Fing
AU - Lin, Shu Fen
AU - Chu, Yen Yi
AU - Miu, Chia Yeh
AU - Lai, Yun Wen
AU - Liu, Hsiang Lin
AU - Her, Jim Long
PY - 2007/8/14
Y1 - 2007/8/14
N2 - 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(MeCN) 4]BF4 or CuX (X = Br, C1) in MeCN. When the reaction mixture of K2TeO3 and [Ru3(CO)12] was first treated with PPh4X followed by the addition of [Cu(MeCN)4]BF4, doubly CuX-bridged Te2Ru 4-based octahedral clusters [PPh4]2[Te 2Ru4(CO)10Cu2X2] (X = Br, [PPh4]2[1]; X = Cl, [PPh4J2P]) 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-TeRu 5-based octahedral cluster compound [PPh4] 2[{TeRu5(CO)14}2Cu 4Cl2] ([PPh4]2[3]). On the other hand, when the reaction mixture of K2TeO3 and [Ru 3(CO)12] was treated with PPh4Br followed by the addition of CuCl, the Cu(Br)CuCl-bridged Te2Ru4-based octahedral cluster chain polymer {[PPh4]2(Te2Ru 4(CO)10-Cu4Br2Cl2)THFL ({[PPh4]2[4]·[THF)∞) was produced. The chain polymer {[PPh4]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.
AB - 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(MeCN) 4]BF4 or CuX (X = Br, C1) in MeCN. When the reaction mixture of K2TeO3 and [Ru3(CO)12] was first treated with PPh4X followed by the addition of [Cu(MeCN)4]BF4, doubly CuX-bridged Te2Ru 4-based octahedral clusters [PPh4]2[Te 2Ru4(CO)10Cu2X2] (X = Br, [PPh4]2[1]; X = Cl, [PPh4J2P]) 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-TeRu 5-based octahedral cluster compound [PPh4] 2[{TeRu5(CO)14}2Cu 4Cl2] ([PPh4]2[3]). On the other hand, when the reaction mixture of K2TeO3 and [Ru 3(CO)12] was treated with PPh4Br followed by the addition of CuCl, the Cu(Br)CuCl-bridged Te2Ru4-based octahedral cluster chain polymer {[PPh4]2(Te2Ru 4(CO)10-Cu4Br2Cl2)THFL ({[PPh4]2[4]·[THF)∞) was produced. The chain polymer {[PPh4]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.
KW - Carbonyl ligands
KW - Cluster compounds
KW - Copper
KW - Ruthenium
KW - Tellurium
UR - http://www.scopus.com/inward/record.url?scp=34547733474&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=34547733474&partnerID=8YFLogxK
U2 - 10.1002/chem.200700135
DO - 10.1002/chem.200700135
M3 - Article
C2 - 17508380
AN - SCOPUS:34547733474
VL - 13
SP - 6605
EP - 6616
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 23
ER -