Controlled synthesis of copper halide-incorporated triiron carbonyl sulfide clusters: Synthesis, electrochemistry, and computational studies

Minghuey Shieh, Chung Yi Huang, Chang Ju Lee, Kai Jieah Hsing, Yu Wei Li, Yen Yi Chu, Wei Ting Jhu

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The reactions of sulfur-capped triiron carbonyl cluster [Et 4N]2[SFe3(CO)9] with 1-6 equiv of copper halides in tetrahydrofuran (THF) at 0 °C led to the formation of a series of CuX-, Cu2X2-, or Cu4X 2-incorporated mono- or di-SFe3-based clusters, [Et 4N]2[SFe3(CO)9CuX] (X = Cl, [Et 4N]2[1a]; Br, [Et4N]2[1b]; I, [Et4N]2[1c]), [Et4N]4[{SFe 3(CO)9CuX}2Cu2X2] (X = Cl, [Et4N]4[2a]; Br, [Et4N]4[2b]), and [Et4N]2[{SFe3(CO)9} 2Cu4X2] (X = Cl, [Et4N] 2[3a]; Br, [Et4N]2[3b]). X-ray analysis showed that each SFe3 core in 1a-1c was bridged by the incoming CuX across the Fe-Fe bond (X = Cl, 1a; Br, 1b; I, 1c); in the case of 2a and 2b, the two SFe3 cores each were bridged by two CuX fragments across the Fe-Fe and S-Fe bonds to form a Cu2X2-linked di-SFe 3CuX cluster (X = Cl, 2a; Br, 2b). In contrast to 2a and 2b, cluster 3a displayed a different di-SFe3-based geometry, in which the two SFe3 moieties were connected by a Cu4Cl2 hexagon. In addition, complexes 1a and 1b were found to undergo cluster expansion reactions to yield 2a and 2b or 3a and 3b upon the treatment of 1 equiv or 3 equiv of CuX (X = Cl, Br), respectively. Furthermore, clusters 2a and 2b could be converted to 3a or 3b upon the addition of 4 equiv of CuX (X = Cl, Br). The nature, formation, and electrochemistry of these copper halide-incorporated mono- or di-SFe3 clusters are elucidated in detail with the aid of molecular calculations at the B3LYP level of the density functional theory in terms of the effects of chalcogens and halides.

Original languageEnglish
Pages (from-to)879-889
Number of pages11
JournalPolyhedron
Volume52
DOIs
Publication statusPublished - 2013 Mar 22

Fingerprint

Electrochemistry
Carbon Monoxide
electrochemistry
halides
sulfides
Copper
copper
X ray analysis
synthesis
Density functional theory
Chalcogens
Sulfur
Geometry
hexagons
tetrahydrofuran
carbonyl sulfide
Sulfides
sulfur
fragments
density functional theory

Keywords

  • Carbonyl
  • Chalcogen
  • Cluster
  • Copper halide
  • Iron

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Controlled synthesis of copper halide-incorporated triiron carbonyl sulfide clusters : Synthesis, electrochemistry, and computational studies. / Shieh, Minghuey; Huang, Chung Yi; Lee, Chang Ju; Hsing, Kai Jieah; Li, Yu Wei; Chu, Yen Yi; Jhu, Wei Ting.

In: Polyhedron, Vol. 52, 22.03.2013, p. 879-889.

Research output: Contribution to journalArticle

Shieh, Minghuey ; Huang, Chung Yi ; Lee, Chang Ju ; Hsing, Kai Jieah ; Li, Yu Wei ; Chu, Yen Yi ; Jhu, Wei Ting. / Controlled synthesis of copper halide-incorporated triiron carbonyl sulfide clusters : Synthesis, electrochemistry, and computational studies. In: Polyhedron. 2013 ; Vol. 52. pp. 879-889.
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title = "Controlled synthesis of copper halide-incorporated triiron carbonyl sulfide clusters: Synthesis, electrochemistry, and computational studies",
abstract = "The reactions of sulfur-capped triiron carbonyl cluster [Et 4N]2[SFe3(CO)9] with 1-6 equiv of copper halides in tetrahydrofuran (THF) at 0 °C led to the formation of a series of CuX-, Cu2X2-, or Cu4X 2-incorporated mono- or di-SFe3-based clusters, [Et 4N]2[SFe3(CO)9CuX] (X = Cl, [Et 4N]2[1a]; Br, [Et4N]2[1b]; I, [Et4N]2[1c]), [Et4N]4[{SFe 3(CO)9CuX}2Cu2X2] (X = Cl, [Et4N]4[2a]; Br, [Et4N]4[2b]), and [Et4N]2[{SFe3(CO)9} 2Cu4X2] (X = Cl, [Et4N] 2[3a]; Br, [Et4N]2[3b]). X-ray analysis showed that each SFe3 core in 1a-1c was bridged by the incoming CuX across the Fe-Fe bond (X = Cl, 1a; Br, 1b; I, 1c); in the case of 2a and 2b, the two SFe3 cores each were bridged by two CuX fragments across the Fe-Fe and S-Fe bonds to form a Cu2X2-linked di-SFe 3CuX cluster (X = Cl, 2a; Br, 2b). In contrast to 2a and 2b, cluster 3a displayed a different di-SFe3-based geometry, in which the two SFe3 moieties were connected by a Cu4Cl2 hexagon. In addition, complexes 1a and 1b were found to undergo cluster expansion reactions to yield 2a and 2b or 3a and 3b upon the treatment of 1 equiv or 3 equiv of CuX (X = Cl, Br), respectively. Furthermore, clusters 2a and 2b could be converted to 3a or 3b upon the addition of 4 equiv of CuX (X = Cl, Br). The nature, formation, and electrochemistry of these copper halide-incorporated mono- or di-SFe3 clusters are elucidated in detail with the aid of molecular calculations at the B3LYP level of the density functional theory in terms of the effects of chalcogens and halides.",
keywords = "Carbonyl, Chalcogen, Cluster, Copper halide, Iron",
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T1 - Controlled synthesis of copper halide-incorporated triiron carbonyl sulfide clusters

T2 - Synthesis, electrochemistry, and computational studies

AU - Shieh, Minghuey

AU - Huang, Chung Yi

AU - Lee, Chang Ju

AU - Hsing, Kai Jieah

AU - Li, Yu Wei

AU - Chu, Yen Yi

AU - Jhu, Wei Ting

PY - 2013/3/22

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N2 - The reactions of sulfur-capped triiron carbonyl cluster [Et 4N]2[SFe3(CO)9] with 1-6 equiv of copper halides in tetrahydrofuran (THF) at 0 °C led to the formation of a series of CuX-, Cu2X2-, or Cu4X 2-incorporated mono- or di-SFe3-based clusters, [Et 4N]2[SFe3(CO)9CuX] (X = Cl, [Et 4N]2[1a]; Br, [Et4N]2[1b]; I, [Et4N]2[1c]), [Et4N]4[{SFe 3(CO)9CuX}2Cu2X2] (X = Cl, [Et4N]4[2a]; Br, [Et4N]4[2b]), and [Et4N]2[{SFe3(CO)9} 2Cu4X2] (X = Cl, [Et4N] 2[3a]; Br, [Et4N]2[3b]). X-ray analysis showed that each SFe3 core in 1a-1c was bridged by the incoming CuX across the Fe-Fe bond (X = Cl, 1a; Br, 1b; I, 1c); in the case of 2a and 2b, the two SFe3 cores each were bridged by two CuX fragments across the Fe-Fe and S-Fe bonds to form a Cu2X2-linked di-SFe 3CuX cluster (X = Cl, 2a; Br, 2b). In contrast to 2a and 2b, cluster 3a displayed a different di-SFe3-based geometry, in which the two SFe3 moieties were connected by a Cu4Cl2 hexagon. In addition, complexes 1a and 1b were found to undergo cluster expansion reactions to yield 2a and 2b or 3a and 3b upon the treatment of 1 equiv or 3 equiv of CuX (X = Cl, Br), respectively. Furthermore, clusters 2a and 2b could be converted to 3a or 3b upon the addition of 4 equiv of CuX (X = Cl, Br). The nature, formation, and electrochemistry of these copper halide-incorporated mono- or di-SFe3 clusters are elucidated in detail with the aid of molecular calculations at the B3LYP level of the density functional theory in terms of the effects of chalcogens and halides.

AB - The reactions of sulfur-capped triiron carbonyl cluster [Et 4N]2[SFe3(CO)9] with 1-6 equiv of copper halides in tetrahydrofuran (THF) at 0 °C led to the formation of a series of CuX-, Cu2X2-, or Cu4X 2-incorporated mono- or di-SFe3-based clusters, [Et 4N]2[SFe3(CO)9CuX] (X = Cl, [Et 4N]2[1a]; Br, [Et4N]2[1b]; I, [Et4N]2[1c]), [Et4N]4[{SFe 3(CO)9CuX}2Cu2X2] (X = Cl, [Et4N]4[2a]; Br, [Et4N]4[2b]), and [Et4N]2[{SFe3(CO)9} 2Cu4X2] (X = Cl, [Et4N] 2[3a]; Br, [Et4N]2[3b]). X-ray analysis showed that each SFe3 core in 1a-1c was bridged by the incoming CuX across the Fe-Fe bond (X = Cl, 1a; Br, 1b; I, 1c); in the case of 2a and 2b, the two SFe3 cores each were bridged by two CuX fragments across the Fe-Fe and S-Fe bonds to form a Cu2X2-linked di-SFe 3CuX cluster (X = Cl, 2a; Br, 2b). In contrast to 2a and 2b, cluster 3a displayed a different di-SFe3-based geometry, in which the two SFe3 moieties were connected by a Cu4Cl2 hexagon. In addition, complexes 1a and 1b were found to undergo cluster expansion reactions to yield 2a and 2b or 3a and 3b upon the treatment of 1 equiv or 3 equiv of CuX (X = Cl, Br), respectively. Furthermore, clusters 2a and 2b could be converted to 3a or 3b upon the addition of 4 equiv of CuX (X = Cl, Br). The nature, formation, and electrochemistry of these copper halide-incorporated mono- or di-SFe3 clusters are elucidated in detail with the aid of molecular calculations at the B3LYP level of the density functional theory in terms of the effects of chalcogens and halides.

KW - Carbonyl

KW - Chalcogen

KW - Cluster

KW - Copper halide

KW - Iron

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