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

doi:10.1021/ic8012552

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

^*Corresponding author for this work

Department of Chemistry

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19 Citations (Scopus)

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 language	English
Pages (from-to)	11018-11031
Number of pages	14
Journal	Inorganic Chemistry
Volume	47
Issue number	23
DOIs	https://doi.org/10.1021/ic8012552
Publication status	Published - 2008 Dec 1

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic8012552

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@article{3f1fec28efb24a8fa9d125b3ef58bec2,

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}",

year = "2008",

month = dec,

day = "1",

doi = "10.1021/ic8012552",

language = "English",

volume = "47",

pages = "11018--11031",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "23",

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TY - JOUR

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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U2 - 10.1021/ic8012552

DO - 10.1021/ic8012552

M3 - Article

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EP - 11031

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 23

ER -

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

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

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CCDC 684594: Experimental Crystal Structure Determination

CCDC 714568: Experimental Crystal Structure Determination

CCDC 684591: Experimental Crystal Structure Determination

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