Reactions of the μ3-sulfido triiron cluster [SFe 3(CO)9]2- with functionalized organic halides and mercury salts: Selective reactivity, electrochemistry, and theoretical calculations

Chia Yeh Miu, Hsin Hung Chi, Szu Wei Chen, Jiann Jang Cherng, Miao Hsing Hsu, Yu Xin Huang, Minghuey Shieh

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Abstract

When the μ3-sulfido triiron cluster [SFe3(CO) 9]2- was treated with BrCH2C(O)OCH3 in MeCN, the ester-functionalized complex [SFe3(CO) 9(CH2C(O)OCH3)]- (1) was obtained. Cluster 1 displays a SFe3 tetrahedral core with one of the Fe atoms bonded to an ester ligand CH2C(O)OCH3. In contrast, when [SFe3(CO)9]2- was treated with dihaloalkanes X(CH2)nX′ (X = Cl, X′ = Br, n = 3; X = X′ = I, n = 4) in MeCN, the sulfur-alkylated complexes [X(CH 2)nSFe3(CO)9]- (X = Cl, n = 3, 2; X = I, n = 4, 3) were formed, respectively. Clusters 2 and 3 each exhibits a SFe3 tetrahedral core with the sulfur atom attached to the halide-functionalized alkyl group. Furthermore, the Hg-bridged di-SFe 3 complex [{SFe3(CO)9} 24-Hg)]2- (4) was isolated from the reaction of [SFe3(CO)9]2- with 2 equiv. of Hg(OAc)2 in acetone. However, when [SFe3(CO) 9]2- was treated with HgI2 under similar conditions, the HgI-bridged cluster [SFe3(CO)9(μ-HgI)] - (5) was produced. In addition, complex 4 could be transformed into complex 3 upon treatment with I(CH2)4I in MeCN. Conversely, complex 3 could be reconverted into 4 in the presence of Hg(OAc)2 in an acetone solution. Clusters 1-5 were fully characterized by spectroscopic methods and single-crystal X-ray analysis. In particular, the nature and selective formation as well as electrochemistry of complexes 1-5, which resulted from the different reactive sites (Fe vs. S atom) of [SFe3(CO)9]2-, were also examined and compared systematically by molecular orbital calculations at the B3LYP level of the density functional theory.

Original languageEnglish
Pages (from-to)2442-2455
Number of pages14
JournalNew Journal of Chemistry
Volume35
Issue number11
DOIs
Publication statusPublished - 2011 Nov

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Electrochemistry
Carbon Monoxide
Mercury
Salts
Acetone
Atoms
Esters
Sulfur
Orbital calculations
X ray analysis
Molecular orbitals
Density functional theory
Ligands
Single crystals

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

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Reactions of the μ3-sulfido triiron cluster [SFe 3(CO)9]2- with functionalized organic halides and mercury salts : Selective reactivity, electrochemistry, and theoretical calculations. / Miu, Chia Yeh; Chi, Hsin Hung; Chen, Szu Wei; Cherng, Jiann Jang; Hsu, Miao Hsing; Huang, Yu Xin; Shieh, Minghuey.

In: New Journal of Chemistry, Vol. 35, No. 11, 11.2011, p. 2442-2455.

Research output: Contribution to journalArticle

Miu, Chia Yeh ; Chi, Hsin Hung ; Chen, Szu Wei ; Cherng, Jiann Jang ; Hsu, Miao Hsing ; Huang, Yu Xin ; Shieh, Minghuey. / Reactions of the μ3-sulfido triiron cluster [SFe 3(CO)9]2- with functionalized organic halides and mercury salts : Selective reactivity, electrochemistry, and theoretical calculations. In: New Journal of Chemistry. 2011 ; Vol. 35, No. 11. pp. 2442-2455.
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title = "Reactions of the μ3-sulfido triiron cluster [SFe 3(CO)9]2- with functionalized organic halides and mercury salts: Selective reactivity, electrochemistry, and theoretical calculations",
abstract = "When the μ3-sulfido triiron cluster [SFe3(CO) 9]2- was treated with BrCH2C(O)OCH3 in MeCN, the ester-functionalized complex [SFe3(CO) 9(CH2C(O)OCH3)]- (1) was obtained. Cluster 1 displays a SFe3 tetrahedral core with one of the Fe atoms bonded to an ester ligand CH2C(O)OCH3. In contrast, when [SFe3(CO)9]2- was treated with dihaloalkanes X(CH2)nX′ (X = Cl, X′ = Br, n = 3; X = X′ = I, n = 4) in MeCN, the sulfur-alkylated complexes [X(CH 2)nSFe3(CO)9]- (X = Cl, n = 3, 2; X = I, n = 4, 3) were formed, respectively. Clusters 2 and 3 each exhibits a SFe3 tetrahedral core with the sulfur atom attached to the halide-functionalized alkyl group. Furthermore, the Hg-bridged di-SFe 3 complex [{SFe3(CO)9} 2(μ4-Hg)]2- (4) was isolated from the reaction of [SFe3(CO)9]2- with 2 equiv. of Hg(OAc)2 in acetone. However, when [SFe3(CO) 9]2- was treated with HgI2 under similar conditions, the HgI-bridged cluster [SFe3(CO)9(μ-HgI)] - (5) was produced. In addition, complex 4 could be transformed into complex 3 upon treatment with I(CH2)4I in MeCN. Conversely, complex 3 could be reconverted into 4 in the presence of Hg(OAc)2 in an acetone solution. Clusters 1-5 were fully characterized by spectroscopic methods and single-crystal X-ray analysis. In particular, the nature and selective formation as well as electrochemistry of complexes 1-5, which resulted from the different reactive sites (Fe vs. S atom) of [SFe3(CO)9]2-, were also examined and compared systematically by molecular orbital calculations at the B3LYP level of the density functional theory.",
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T1 - Reactions of the μ3-sulfido triiron cluster [SFe 3(CO)9]2- with functionalized organic halides and mercury salts

T2 - Selective reactivity, electrochemistry, and theoretical calculations

AU - Miu, Chia Yeh

AU - Chi, Hsin Hung

AU - Chen, Szu Wei

AU - Cherng, Jiann Jang

AU - Hsu, Miao Hsing

AU - Huang, Yu Xin

AU - Shieh, Minghuey

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N2 - When the μ3-sulfido triiron cluster [SFe3(CO) 9]2- was treated with BrCH2C(O)OCH3 in MeCN, the ester-functionalized complex [SFe3(CO) 9(CH2C(O)OCH3)]- (1) was obtained. Cluster 1 displays a SFe3 tetrahedral core with one of the Fe atoms bonded to an ester ligand CH2C(O)OCH3. In contrast, when [SFe3(CO)9]2- was treated with dihaloalkanes X(CH2)nX′ (X = Cl, X′ = Br, n = 3; X = X′ = I, n = 4) in MeCN, the sulfur-alkylated complexes [X(CH 2)nSFe3(CO)9]- (X = Cl, n = 3, 2; X = I, n = 4, 3) were formed, respectively. Clusters 2 and 3 each exhibits a SFe3 tetrahedral core with the sulfur atom attached to the halide-functionalized alkyl group. Furthermore, the Hg-bridged di-SFe 3 complex [{SFe3(CO)9} 2(μ4-Hg)]2- (4) was isolated from the reaction of [SFe3(CO)9]2- with 2 equiv. of Hg(OAc)2 in acetone. However, when [SFe3(CO) 9]2- was treated with HgI2 under similar conditions, the HgI-bridged cluster [SFe3(CO)9(μ-HgI)] - (5) was produced. In addition, complex 4 could be transformed into complex 3 upon treatment with I(CH2)4I in MeCN. Conversely, complex 3 could be reconverted into 4 in the presence of Hg(OAc)2 in an acetone solution. Clusters 1-5 were fully characterized by spectroscopic methods and single-crystal X-ray analysis. In particular, the nature and selective formation as well as electrochemistry of complexes 1-5, which resulted from the different reactive sites (Fe vs. S atom) of [SFe3(CO)9]2-, were also examined and compared systematically by molecular orbital calculations at the B3LYP level of the density functional theory.

AB - When the μ3-sulfido triiron cluster [SFe3(CO) 9]2- was treated with BrCH2C(O)OCH3 in MeCN, the ester-functionalized complex [SFe3(CO) 9(CH2C(O)OCH3)]- (1) was obtained. Cluster 1 displays a SFe3 tetrahedral core with one of the Fe atoms bonded to an ester ligand CH2C(O)OCH3. In contrast, when [SFe3(CO)9]2- was treated with dihaloalkanes X(CH2)nX′ (X = Cl, X′ = Br, n = 3; X = X′ = I, n = 4) in MeCN, the sulfur-alkylated complexes [X(CH 2)nSFe3(CO)9]- (X = Cl, n = 3, 2; X = I, n = 4, 3) were formed, respectively. Clusters 2 and 3 each exhibits a SFe3 tetrahedral core with the sulfur atom attached to the halide-functionalized alkyl group. Furthermore, the Hg-bridged di-SFe 3 complex [{SFe3(CO)9} 2(μ4-Hg)]2- (4) was isolated from the reaction of [SFe3(CO)9]2- with 2 equiv. of Hg(OAc)2 in acetone. However, when [SFe3(CO) 9]2- was treated with HgI2 under similar conditions, the HgI-bridged cluster [SFe3(CO)9(μ-HgI)] - (5) was produced. In addition, complex 4 could be transformed into complex 3 upon treatment with I(CH2)4I in MeCN. Conversely, complex 3 could be reconverted into 4 in the presence of Hg(OAc)2 in an acetone solution. Clusters 1-5 were fully characterized by spectroscopic methods and single-crystal X-ray analysis. In particular, the nature and selective formation as well as electrochemistry of complexes 1-5, which resulted from the different reactive sites (Fe vs. S atom) of [SFe3(CO)9]2-, were also examined and compared systematically by molecular orbital calculations at the B3LYP level of the density functional theory.

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