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

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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
Publication statusPublished - 2013 Mar 22



  • Carbonyl
  • Chalcogen
  • Cluster
  • Copper halide
  • Iron

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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