Copper halide-lncorporated tellurium-iron carbonyl complexes: Transformation, electrochemical properties, and theoretical calculations

Bo Gaun Chen, Chia Hua Ho, Chang Ju Lee, Minghuey Shieh

Research output: Contribution to journalArticle

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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 languageEnglish
Pages (from-to)10757-10768
Number of pages12
JournalInorganic Chemistry
Volume48
Issue number22
DOIs
Publication statusPublished - 2009 Nov 16

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Tellurium
tellurium
Carbon Monoxide
Electrochemical properties
halides
Copper
Iron
X ray analysis
iron
copper
X-Rays
Skeleton
tetrahydrofuran
Electrochemistry
musculoskeletal system
Density functional theory
x rays
Metals
Atoms
Temperature

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 journalArticle

@article{9a0218c0cd4846d6b9ab9d2368393dff,
title = "Copper halide-lncorporated tellurium-iron carbonyl complexes: Transformation, electrochemical properties, and theoretical calculations",
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.",
author = "Chen, {Bo Gaun} and Ho, {Chia Hua} and Lee, {Chang Ju} and Minghuey Shieh",
year = "2009",
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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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