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

doi:10.1021/ic200885h

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

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

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 language	English
Pages (from-to)	7735-7748
Number of pages	14
Journal	Inorganic Chemistry
Volume	50
Issue number	16
DOIs	https://doi.org/10.1021/ic200885h
Publication status	Published - 2011 Aug 15

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic200885h

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@article{14573f3c0f934288adb80a8985f8dc02,

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.",

author = "Minghuey Shieh and Miu, {Chia Yeh} and Huang, {Kuo Chih} and Lee, {Chung Feng} and Chen, {Bao Gun}",

year = "2011",

month = aug,

day = "15",

doi = "10.1021/ic200885h",

language = "English",

volume = "50",

pages = "7735--7748",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Stepwise construction of manganese-chromium carbonyl chalcogenide complexes

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

Y1 - 2011/8/15

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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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 16

ER -

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

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

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CCDC 844221: Experimental Crystal Structure Determination

CCDC 844219: Experimental Crystal Structure Determination

CCDC 844220: Experimental Crystal Structure Determination

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