Stepwise construction of manganese-chromium carbonyl chalcogenide complexes: Synthesis, electrochemical properties, and computational studies

Minghuey Shieh, Chia Yeh Miu, Kuo Chih Huang, Chung Feng Lee, Bao Gun Chen

Research output: Contribution to journalArticle

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Abstract

When trigonal-bipyramidal clusters, [PPN][E2Mn 3(CO)9] (E = S, Se), were treated with Cr(CO)6 and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)5-incorporated HE2Mn3-complexes [PPN]2[HE2Mn3Cr(CO)14] (E = S, [PPN]2[1a]; Se, [PPN]2[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E2Mn3 square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)5 group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA + salts for [E2Mn3(CO)9]- were mixed with Cr(CO)6 in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)3-incorporated E 2Mn3Cr octahedral clusters [TMBA]3[E 2Mn3Cr(CO)12] (E = S, [TMBA]3[2a]; Se, [TMBA]3[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E2Mn 3Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn3Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)5-incorporated HE 2Mn3-clusters [HE2Mn3Cr 2(CO)19]2- (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)6 heated in refluxing CH2Cl2. Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)5 group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the density functional theory.

Original languageEnglish
Pages (from-to)7735-7748
Number of pages14
JournalInorganic Chemistry
Volume50
Issue number16
DOIs
Publication statusPublished - 2011 Aug 15

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electrochemical synthesis
Carbon Monoxide
Manganese
Electrochemical properties
manganese
chromium
chromium hexacarbonyl
Atoms
salts
Chalcogens
Salts
Metals
selenides
musculoskeletal system
metals
closures
atoms
sulfides
hydrogen atoms
Skeleton

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Stepwise construction of manganese-chromium carbonyl chalcogenide complexes : Synthesis, electrochemical properties, and computational studies. / Shieh, Minghuey; Miu, Chia Yeh; Huang, Kuo Chih; Lee, Chung Feng; Chen, Bao Gun.

In: Inorganic Chemistry, Vol. 50, No. 16, 15.08.2011, p. 7735-7748.

Research output: Contribution to journalArticle

Shieh, Minghuey ; Miu, Chia Yeh ; Huang, Kuo Chih ; Lee, Chung Feng ; Chen, Bao Gun. / Stepwise construction of manganese-chromium carbonyl chalcogenide complexes : Synthesis, electrochemical properties, and computational studies. In: Inorganic Chemistry. 2011 ; Vol. 50, No. 16. pp. 7735-7748.
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title = "Stepwise construction of manganese-chromium carbonyl chalcogenide complexes: Synthesis, electrochemical properties, and computational studies",
abstract = "When trigonal-bipyramidal clusters, [PPN][E2Mn 3(CO)9] (E = S, Se), were treated with Cr(CO)6 and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)5-incorporated HE2Mn3-complexes [PPN]2[HE2Mn3Cr(CO)14] (E = S, [PPN]2[1a]; Se, [PPN]2[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E2Mn3 square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)5 group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA + salts for [E2Mn3(CO)9]- were mixed with Cr(CO)6 in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)3-incorporated E 2Mn3Cr octahedral clusters [TMBA]3[E 2Mn3Cr(CO)12] (E = S, [TMBA]3[2a]; Se, [TMBA]3[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E2Mn 3Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn3Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)5-incorporated HE 2Mn3-clusters [HE2Mn3Cr 2(CO)19]2- (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)6 heated in refluxing CH2Cl2. Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)5 group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the density functional theory.",
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T2 - Synthesis, electrochemical properties, and computational studies

AU - Shieh, Minghuey

AU - Miu, Chia Yeh

AU - Huang, Kuo Chih

AU - Lee, Chung Feng

AU - Chen, Bao Gun

PY - 2011/8/15

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N2 - When trigonal-bipyramidal clusters, [PPN][E2Mn 3(CO)9] (E = S, Se), were treated with Cr(CO)6 and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)5-incorporated HE2Mn3-complexes [PPN]2[HE2Mn3Cr(CO)14] (E = S, [PPN]2[1a]; Se, [PPN]2[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E2Mn3 square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)5 group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA + salts for [E2Mn3(CO)9]- were mixed with Cr(CO)6 in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)3-incorporated E 2Mn3Cr octahedral clusters [TMBA]3[E 2Mn3Cr(CO)12] (E = S, [TMBA]3[2a]; Se, [TMBA]3[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E2Mn 3Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn3Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)5-incorporated HE 2Mn3-clusters [HE2Mn3Cr 2(CO)19]2- (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)6 heated in refluxing CH2Cl2. Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)5 group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the density functional theory.

AB - When trigonal-bipyramidal clusters, [PPN][E2Mn 3(CO)9] (E = S, Se), were treated with Cr(CO)6 and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)5-incorporated HE2Mn3-complexes [PPN]2[HE2Mn3Cr(CO)14] (E = S, [PPN]2[1a]; Se, [PPN]2[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E2Mn3 square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)5 group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA + salts for [E2Mn3(CO)9]- were mixed with Cr(CO)6 in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)3-incorporated E 2Mn3Cr octahedral clusters [TMBA]3[E 2Mn3Cr(CO)12] (E = S, [TMBA]3[2a]; Se, [TMBA]3[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E2Mn 3Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn3Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)5-incorporated HE 2Mn3-clusters [HE2Mn3Cr 2(CO)19]2- (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)6 heated in refluxing CH2Cl2. Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)5 group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the density functional theory.

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