Construction of copper halide-triiron selenide carbonyl complexes: Synthetic, electrochemical, and theoretical studies

Minghuey Shieh, Chia Yeh Miu, Chang Ju Lee, Wei G. Chen, Yen Yi Chu, Hui Lung Chen

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Abstract

A new family of CuX-, Cu2X2-, and Cu 4X2-incorporated mono- or di-SeFe3-based carbonyl clusters were constructed and structurally characterized. When the selenium-capped triiron carbonyl cluster [Et4N]2[SeFe 3(CO)9] was treated with 1-3 equiv of CuX in tetrahydrofuran (THF) at low or room temperatures, CuX-incorporated SeFe 3 complexes [Et4N]2[SeFe3(CO) 9CuX] (X = Cl, [Et4N]2[1a]; Br, [Et 4N]2[1b]; I, [Et4N]2[1c]), Cu 2X2-incorporated SeFe3 clusters [Et 4N]2[SeFe3(CO)9Cu2X 2] (X = Cl, [Et4N]2[2a]; Br, [Et 4N]2[2b]), and Cu4X2-linked di-SeFe3 clusters [Et4N]2[{SeFe 3(CO)9}2Cu4X2] (X = Cl, [Et4N]2[3a]; Br, [PPh4]2[3b]) were obtained, respectively, in good yields. SeFe3CuX complexes 1a and 1b were found to undergo cluster expansion to form SeFe3Cu 2X2 complexes 2a and 2b, respectively, upon the addition of 1 equiv of CuX (X = Cl, Br). Furthermore, complexes 2a and 2b can expand further to form Cu4X2-linked di-SeFe3 clusters 3a and 3b, upon treatment with 1 equiv of CuX (X = Cl, Br). [Et 4N]4[{SeFe3(CO)9(CuCl) 2}2] ([Et4N]4[4a]) was produced when the reaction of [Et4N]2[SeFe3(CO)9] with 2 equiv of CuCl was conducted in THF at 40°C. The Cu 2Cl2-linked di-SeFe3CuCl cluster 4a is a dimerization product derived from complex 2a. Further, it is found that complex 4a can convert to the Cu4Cl2-linked di-SeFe3 cluster 3a upon treatment with CuCl. The nature, formation, stepwise cluster expansion, and electrochemical properties of these CuX-, Cu2X 2-, and Cu4X2-incorporated mono- or di-SeFe3-based clusters are elucidated in detail by molecular calculations at the B3LYP level of the density functional theory in terms of the effects of selenium, iron, copper halides, and the size of the metal skeleton.

Original languageEnglish
Pages (from-to)11018-11031
Number of pages14
JournalInorganic Chemistry
Volume47
Issue number23
DOIs
Publication statusPublished - 2008 Dec 1

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selenides
Carbon Monoxide
halides
Copper
Theoretical Models
copper
Selenium
tetrahydrofuran
selenium
Dimerization
Electrochemical properties
Skeleton
Density functional theory
Iron
Metals
expansion
dimerization
Temperature
musculoskeletal system
density functional theory

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Construction of copper halide-triiron selenide carbonyl complexes : Synthetic, electrochemical, and theoretical studies. / Shieh, Minghuey; Miu, Chia Yeh; Lee, Chang Ju; Chen, Wei G.; Chu, Yen Yi; Chen, Hui Lung.

In: Inorganic Chemistry, Vol. 47, No. 23, 01.12.2008, p. 11018-11031.

Research output: Contribution to journalArticle

Shieh, Minghuey ; Miu, Chia Yeh ; Lee, Chang Ju ; Chen, Wei G. ; Chu, Yen Yi ; Chen, Hui Lung. / Construction of copper halide-triiron selenide carbonyl complexes : Synthetic, electrochemical, and theoretical studies. In: Inorganic Chemistry. 2008 ; Vol. 47, No. 23. pp. 11018-11031.
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title = "Construction of copper halide-triiron selenide carbonyl complexes: Synthetic, electrochemical, and theoretical studies",
abstract = "A new family of CuX-, Cu2X2-, and Cu 4X2-incorporated mono- or di-SeFe3-based carbonyl clusters were constructed and structurally characterized. When the selenium-capped triiron carbonyl cluster [Et4N]2[SeFe 3(CO)9] was treated with 1-3 equiv of CuX in tetrahydrofuran (THF) at low or room temperatures, CuX-incorporated SeFe 3 complexes [Et4N]2[SeFe3(CO) 9CuX] (X = Cl, [Et4N]2[1a]; Br, [Et 4N]2[1b]; I, [Et4N]2[1c]), Cu 2X2-incorporated SeFe3 clusters [Et 4N]2[SeFe3(CO)9Cu2X 2] (X = Cl, [Et4N]2[2a]; Br, [Et 4N]2[2b]), and Cu4X2-linked di-SeFe3 clusters [Et4N]2[{SeFe 3(CO)9}2Cu4X2] (X = Cl, [Et4N]2[3a]; Br, [PPh4]2[3b]) were obtained, respectively, in good yields. SeFe3CuX complexes 1a and 1b were found to undergo cluster expansion to form SeFe3Cu 2X2 complexes 2a and 2b, respectively, upon the addition of 1 equiv of CuX (X = Cl, Br). Furthermore, complexes 2a and 2b can expand further to form Cu4X2-linked di-SeFe3 clusters 3a and 3b, upon treatment with 1 equiv of CuX (X = Cl, Br). [Et 4N]4[{SeFe3(CO)9(CuCl) 2}2] ([Et4N]4[4a]) was produced when the reaction of [Et4N]2[SeFe3(CO)9] with 2 equiv of CuCl was conducted in THF at 40°C. The Cu 2Cl2-linked di-SeFe3CuCl cluster 4a is a dimerization product derived from complex 2a. Further, it is found that complex 4a can convert to the Cu4Cl2-linked di-SeFe3 cluster 3a upon treatment with CuCl. The nature, formation, stepwise cluster expansion, and electrochemical properties of these CuX-, Cu2X 2-, and Cu4X2-incorporated mono- or di-SeFe3-based clusters are elucidated in detail by molecular calculations at the B3LYP level of the density functional theory in terms of the effects of selenium, iron, copper halides, and the size of the metal skeleton.",
author = "Minghuey Shieh and Miu, {Chia Yeh} and Lee, {Chang Ju} and Chen, {Wei G.} and Chu, {Yen Yi} and Chen, {Hui Lung}",
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T1 - Construction of copper halide-triiron selenide carbonyl complexes

T2 - Synthetic, electrochemical, and theoretical studies

AU - Shieh, Minghuey

AU - Miu, Chia Yeh

AU - Lee, Chang Ju

AU - Chen, Wei G.

AU - Chu, Yen Yi

AU - Chen, Hui Lung

PY - 2008/12/1

Y1 - 2008/12/1

N2 - A new family of CuX-, Cu2X2-, and Cu 4X2-incorporated mono- or di-SeFe3-based carbonyl clusters were constructed and structurally characterized. When the selenium-capped triiron carbonyl cluster [Et4N]2[SeFe 3(CO)9] was treated with 1-3 equiv of CuX in tetrahydrofuran (THF) at low or room temperatures, CuX-incorporated SeFe 3 complexes [Et4N]2[SeFe3(CO) 9CuX] (X = Cl, [Et4N]2[1a]; Br, [Et 4N]2[1b]; I, [Et4N]2[1c]), Cu 2X2-incorporated SeFe3 clusters [Et 4N]2[SeFe3(CO)9Cu2X 2] (X = Cl, [Et4N]2[2a]; Br, [Et 4N]2[2b]), and Cu4X2-linked di-SeFe3 clusters [Et4N]2[{SeFe 3(CO)9}2Cu4X2] (X = Cl, [Et4N]2[3a]; Br, [PPh4]2[3b]) were obtained, respectively, in good yields. SeFe3CuX complexes 1a and 1b were found to undergo cluster expansion to form SeFe3Cu 2X2 complexes 2a and 2b, respectively, upon the addition of 1 equiv of CuX (X = Cl, Br). Furthermore, complexes 2a and 2b can expand further to form Cu4X2-linked di-SeFe3 clusters 3a and 3b, upon treatment with 1 equiv of CuX (X = Cl, Br). [Et 4N]4[{SeFe3(CO)9(CuCl) 2}2] ([Et4N]4[4a]) was produced when the reaction of [Et4N]2[SeFe3(CO)9] with 2 equiv of CuCl was conducted in THF at 40°C. The Cu 2Cl2-linked di-SeFe3CuCl cluster 4a is a dimerization product derived from complex 2a. Further, it is found that complex 4a can convert to the Cu4Cl2-linked di-SeFe3 cluster 3a upon treatment with CuCl. The nature, formation, stepwise cluster expansion, and electrochemical properties of these CuX-, Cu2X 2-, and Cu4X2-incorporated mono- or di-SeFe3-based clusters are elucidated in detail by molecular calculations at the B3LYP level of the density functional theory in terms of the effects of selenium, iron, copper halides, and the size of the metal skeleton.

AB - A new family of CuX-, Cu2X2-, and Cu 4X2-incorporated mono- or di-SeFe3-based carbonyl clusters were constructed and structurally characterized. When the selenium-capped triiron carbonyl cluster [Et4N]2[SeFe 3(CO)9] was treated with 1-3 equiv of CuX in tetrahydrofuran (THF) at low or room temperatures, CuX-incorporated SeFe 3 complexes [Et4N]2[SeFe3(CO) 9CuX] (X = Cl, [Et4N]2[1a]; Br, [Et 4N]2[1b]; I, [Et4N]2[1c]), Cu 2X2-incorporated SeFe3 clusters [Et 4N]2[SeFe3(CO)9Cu2X 2] (X = Cl, [Et4N]2[2a]; Br, [Et 4N]2[2b]), and Cu4X2-linked di-SeFe3 clusters [Et4N]2[{SeFe 3(CO)9}2Cu4X2] (X = Cl, [Et4N]2[3a]; Br, [PPh4]2[3b]) were obtained, respectively, in good yields. SeFe3CuX complexes 1a and 1b were found to undergo cluster expansion to form SeFe3Cu 2X2 complexes 2a and 2b, respectively, upon the addition of 1 equiv of CuX (X = Cl, Br). Furthermore, complexes 2a and 2b can expand further to form Cu4X2-linked di-SeFe3 clusters 3a and 3b, upon treatment with 1 equiv of CuX (X = Cl, Br). [Et 4N]4[{SeFe3(CO)9(CuCl) 2}2] ([Et4N]4[4a]) was produced when the reaction of [Et4N]2[SeFe3(CO)9] with 2 equiv of CuCl was conducted in THF at 40°C. The Cu 2Cl2-linked di-SeFe3CuCl cluster 4a is a dimerization product derived from complex 2a. Further, it is found that complex 4a can convert to the Cu4Cl2-linked di-SeFe3 cluster 3a upon treatment with CuCl. The nature, formation, stepwise cluster expansion, and electrochemical properties of these CuX-, Cu2X 2-, and Cu4X2-incorporated mono- or di-SeFe3-based clusters are elucidated in detail by molecular calculations at the B3LYP level of the density functional theory in terms of the effects of selenium, iron, copper halides, and the size of the metal skeleton.

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