Abstract
When the tellurium-capped tri-iron carbonyl cluster [Et 4 N] 2 [TeFe 3 (CO) 9 ] was treated with 1 equiv of CuX In THF at O °C, CuX-incorporated clusters [Et 4 N] 2 [TeFe 3 (CO) 9 CuX] (X= Cl, [Et 4 N] 2 [1a]; Br, [Et 4 N] 2 [1b]; I, [Et 4 N] 2 [1c]) were formed, respectively. X-ray analysis showed that 1a-1c each exhibited a TeFe3 core with one Fe-Fe bond bridged by one CuX fragment. When the reactions were carried out at a molar ratio of 1:2 (X= Cl, Br) or 1:3 (X= I) In tetrahydrofuran (THF) or MeCN at O °C, Cu 2 X 2 -lncorporated clusters [Et 4 N] 2 [TeFe 3 (CO) 9 Cu 2 X 2 ] (X= Cl, [Et 4 N] 2 [2a]; Br, [Et 4 N] 2 [2b]; I, [Et 4 N] 2 [2c]) were obtained, respectively. Cluster 2a was structurally characterized by X-ray analysis to display a TeFe 3 core, In which one TeFe 2 plane was asymmetrically bridged and capped by one μ 3 -CuCl and another μ 4 -CuCI with two Cu atoms bonded. Complexes 1a-1c underwent skeleton expansion to form Cu 3 Xincorporated di-TeFe 3 clusters [(TeFe 3 (CO) 9 } 2 Cu 3 X] 2- (X= Cl, 3a; Br, 3b; 1,3c), respectively, upon treatment with 1 equiv of [Cu(MeCN) 4 ][BF 4 ] at O °C. X-ray analysis snowed that 3b and 3c each consisted of two TeFe3 clusters that were linked by a Cu 3 X moiety. However, a similar reaction for 1a and 1b with 1 equiv of [Cu(MeCN) 4 ][BF 4 ] at room temperature produced Cu 4 X 2 -llnked di-TeFe3 clusters [(TeFe 3 (CO) 9 } 2 Cu 4 X 2 ] 2- (X= Cl, 4a; Br, 4b). Cluster 4a was shown by X-ray analysis to have two TeFe3 cores linked by a Cu 4 Cl 2 moiety. Clusters 4a and 4b were also produced directly from the reaction of [Et 4 N] 2 [TeFe 3 (CO) 9 ] with 4 equiv of CuX (X= Cl, Br) In THF. Furthermore, the nature, the formation, the cluster transformation, and the electrochemistry of the CuX-incorporated mono- or di-TeFe 3 clusters are explained in terms of the effects of tellurium, copper hallde, and the size of the metal skeleton, all of which are elucidated by molecular calculations at the B3LYP level of density functional theory.
| Original language | English |
|---|---|
| Pages (from-to) | 10757-10768 |
| Number of pages | 12 |
| Journal | Inorganic Chemistry |
| Volume | 48 |
| Issue number | 22 |
| DOIs | |
| Publication status | Published - 2009 Nov 16 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
Cite this
Copper halide-lncorporated tellurium-iron carbonyl complexes : Transformation, electrochemical properties, and theoretical calculations. / Chen, Bo Gaun; Ho, Chia Hua; Lee, Chang Ju; Shieh, Minghuey.
In: Inorganic Chemistry, Vol. 48, No. 22, 16.11.2009, p. 10757-10768.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Copper halide-lncorporated tellurium-iron carbonyl complexes
T2 - Transformation, electrochemical properties, and theoretical calculations
AU - Chen, Bo Gaun
AU - Ho, Chia Hua
AU - Lee, Chang Ju
AU - Shieh, Minghuey
PY - 2009/11/16
Y1 - 2009/11/16
N2 - When the tellurium-capped tri-iron carbonyl cluster [Et 4 N] 2 [TeFe 3 (CO) 9 ] was treated with 1 equiv of CuX In THF at O °C, CuX-incorporated clusters [Et 4 N] 2 [TeFe 3 (CO) 9 CuX] (X= Cl, [Et 4 N] 2 [1a]; Br, [Et 4 N] 2 [1b]; I, [Et 4 N] 2 [1c]) were formed, respectively. X-ray analysis showed that 1a-1c each exhibited a TeFe3 core with one Fe-Fe bond bridged by one CuX fragment. When the reactions were carried out at a molar ratio of 1:2 (X= Cl, Br) or 1:3 (X= I) In tetrahydrofuran (THF) or MeCN at O °C, Cu 2 X 2 -lncorporated clusters [Et 4 N] 2 [TeFe 3 (CO) 9 Cu 2 X 2 ] (X= Cl, [Et 4 N] 2 [2a]; Br, [Et 4 N] 2 [2b]; I, [Et 4 N] 2 [2c]) were obtained, respectively. Cluster 2a was structurally characterized by X-ray analysis to display a TeFe 3 core, In which one TeFe 2 plane was asymmetrically bridged and capped by one μ 3 -CuCl and another μ 4 -CuCI with two Cu atoms bonded. Complexes 1a-1c underwent skeleton expansion to form Cu 3 Xincorporated di-TeFe 3 clusters [(TeFe 3 (CO) 9 } 2 Cu 3 X] 2- (X= Cl, 3a; Br, 3b; 1,3c), respectively, upon treatment with 1 equiv of [Cu(MeCN) 4 ][BF 4 ] at O °C. X-ray analysis snowed that 3b and 3c each consisted of two TeFe3 clusters that were linked by a Cu 3 X moiety. However, a similar reaction for 1a and 1b with 1 equiv of [Cu(MeCN) 4 ][BF 4 ] at room temperature produced Cu 4 X 2 -llnked di-TeFe3 clusters [(TeFe 3 (CO) 9 } 2 Cu 4 X 2 ] 2- (X= Cl, 4a; Br, 4b). Cluster 4a was shown by X-ray analysis to have two TeFe3 cores linked by a Cu 4 Cl 2 moiety. Clusters 4a and 4b were also produced directly from the reaction of [Et 4 N] 2 [TeFe 3 (CO) 9 ] with 4 equiv of CuX (X= Cl, Br) In THF. Furthermore, the nature, the formation, the cluster transformation, and the electrochemistry of the CuX-incorporated mono- or di-TeFe 3 clusters are explained in terms of the effects of tellurium, copper hallde, and the size of the metal skeleton, all of which are elucidated by molecular calculations at the B3LYP level of density functional theory.
AB - When the tellurium-capped tri-iron carbonyl cluster [Et 4 N] 2 [TeFe 3 (CO) 9 ] was treated with 1 equiv of CuX In THF at O °C, CuX-incorporated clusters [Et 4 N] 2 [TeFe 3 (CO) 9 CuX] (X= Cl, [Et 4 N] 2 [1a]; Br, [Et 4 N] 2 [1b]; I, [Et 4 N] 2 [1c]) were formed, respectively. X-ray analysis showed that 1a-1c each exhibited a TeFe3 core with one Fe-Fe bond bridged by one CuX fragment. When the reactions were carried out at a molar ratio of 1:2 (X= Cl, Br) or 1:3 (X= I) In tetrahydrofuran (THF) or MeCN at O °C, Cu 2 X 2 -lncorporated clusters [Et 4 N] 2 [TeFe 3 (CO) 9 Cu 2 X 2 ] (X= Cl, [Et 4 N] 2 [2a]; Br, [Et 4 N] 2 [2b]; I, [Et 4 N] 2 [2c]) were obtained, respectively. Cluster 2a was structurally characterized by X-ray analysis to display a TeFe 3 core, In which one TeFe 2 plane was asymmetrically bridged and capped by one μ 3 -CuCl and another μ 4 -CuCI with two Cu atoms bonded. Complexes 1a-1c underwent skeleton expansion to form Cu 3 Xincorporated di-TeFe 3 clusters [(TeFe 3 (CO) 9 } 2 Cu 3 X] 2- (X= Cl, 3a; Br, 3b; 1,3c), respectively, upon treatment with 1 equiv of [Cu(MeCN) 4 ][BF 4 ] at O °C. X-ray analysis snowed that 3b and 3c each consisted of two TeFe3 clusters that were linked by a Cu 3 X moiety. However, a similar reaction for 1a and 1b with 1 equiv of [Cu(MeCN) 4 ][BF 4 ] at room temperature produced Cu 4 X 2 -llnked di-TeFe3 clusters [(TeFe 3 (CO) 9 } 2 Cu 4 X 2 ] 2- (X= Cl, 4a; Br, 4b). Cluster 4a was shown by X-ray analysis to have two TeFe3 cores linked by a Cu 4 Cl 2 moiety. Clusters 4a and 4b were also produced directly from the reaction of [Et 4 N] 2 [TeFe 3 (CO) 9 ] with 4 equiv of CuX (X= Cl, Br) In THF. Furthermore, the nature, the formation, the cluster transformation, and the electrochemistry of the CuX-incorporated mono- or di-TeFe 3 clusters are explained in terms of the effects of tellurium, copper hallde, and the size of the metal skeleton, all of which are elucidated by molecular calculations at the B3LYP level of density functional theory.
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UR - http://www.scopus.com/inward/citedby.url?scp=70450186704&partnerID=8YFLogxK
U2 - 10.1021/ic901647n
DO - 10.1021/ic901647n
M3 - Article
C2 - 19831367
AN - SCOPUS:70450186704
VL - 48
SP - 10757
EP - 10768
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 22
ER -