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 language | English |
|---|---|
| Pages (from-to) | 879-889 |
| Number of pages | 11 |
| Journal | Polyhedron |
| Volume | 52 |
| DOIs | |
| Publication status | Published - 2013 Mar 22 |
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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 journal › Article
}
TY - JOUR
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
Y1 - 2013/3/22
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
UR - http://www.scopus.com/inward/record.url?scp=84875449729&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84875449729&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2012.07.026
DO - 10.1016/j.poly.2012.07.026
M3 - Article
AN - SCOPUS:84875449729
VL - 52
SP - 879
EP - 889
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
ER -