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
N1 - Funding Information:
This work was supported by the National Science Council of Taiwan (NSC Grant No. 98-2113-M-003-006-MY3 to M. Shieh). We are also grateful to the National Center for High-Performance Computing, where the Gaussian package and computer time were provided.
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
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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 -