Selenium-manganese carbonyl clusters: Synthesis, reversible transformation, electrochemical properties, and theoretical calculations

Chia Hua Ho; Yen Yi Chu; Chien Nan Lin; Horng Wen Chen; Chung Yi Huang; Minghuey Shieh

doi:10.1021/om1006819

Selenium-manganese carbonyl clusters: Synthesis, reversible transformation, electrochemical properties, and theoretical calculations

Chia Hua Ho, Yen Yi Chu, Chien Nan Lin, Horng Wen Chen, Chung Yi Huang, Minghuey Shieh^*

^*Corresponding author for this work

Department of Chemistry

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

13 Citations (Scopus)

Abstract

The reaction of Se₈ with 6 equiv of Mn₂(CO) ₁₀ in concentrated KOH/MeOH solutions led to the formation of the odd-electron cluster [Se₂Mn₃(CO)₉]^2- (1), which was oxidized with [Cu(MeCN)₄][BF₄] to give the oxidation product [Se₂Mn₃(CO)₉]^- (2). Cluster 2 could be reconverted into cluster 1 by the addition of 4 M KOH/MeOH solutions in MeCN. While the trigonal-bipyramidal cluster 2 underwent cluster expansion to give rise to the large Se-inserted cluster [Se ₆Mn₆(CO)₁₈]^4- (3) upon the reaction with a 1/8 equiv of Se₈ in KOH/MeOH solutions, the square-pyramidal cluster 1 was transformed into the even larger Se-rich cluster [Se ₁₀Mn₆(CO)₁₈]^4- (4) upon the addition of a 3/8 equiv of Se₈ in MeOH. Cluster 3 underwent cluster expansion to form cluster 4 when treated with an additional 1/2 equiv of Se₈ in MeCN. Conversely, cluster 4 was selectively reconverted into cluster 1 or 3 upon treatment with 4 or 2 equiv of Mn₂(CO)₁₀ in KOH/MeOH solutions, respectively. On the other hand, the Se₆Mn₆ cluster 3 was transformed into cluster 1 when treated with 2 equiv of Mn ₂(CO)₁₀ in KOH/MeOH solutions. Furthermore, when cluster 3 was treated with [Cu(MeCN)₄][BF₄] or Mn(CO) ₅Br, cluster 2 and/or [Se₅Mn₄(CO) ₁₂]^2- (5) were obtained. X-ray analysis showed that cluster 5 consisted of four Mn(CO)₃ fragments, which were further connected by one μ₃-Se and two μ₃- and μ₄-Se₂ moieties to give a nest-like cluster. Moreover, Se₁₀Mn₆ cluster 4 could also be transformed into cluster 5 upon reaction with [Cu(MeCN)₄][BF₄] or Mn(CO) ₅Br. After a long reaction time, a new picnic-basket-like cluster, [Se₄Mn₃(CO)₁₀]^- (6), formed, which was also obtained from cluster 5 with [Cu(MeCN)₄][BF₄] or Mn(CO)₅Br. Furthermore, the nature, cluster transformation and interconversion, and electrochemical properties of these Se-Mn-CO clusters were elucidated by molecular calculations at the B3PW91 level of the density functional theory.

Original language	English
Pages (from-to)	4396-4405
Number of pages	10
Journal	Organometallics
Volume	29
Issue number	19
DOIs	https://doi.org/10.1021/om1006819
Publication status	Published - 2010 Oct 11

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om1006819

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@article{b3940bfe7584479c9646f141f5d872fa,

title = "Selenium-manganese carbonyl clusters: Synthesis, reversible transformation, electrochemical properties, and theoretical calculations",

abstract = "The reaction of Se8 with 6 equiv of Mn2(CO) 10 in concentrated KOH/MeOH solutions led to the formation of the odd-electron cluster [Se2Mn3(CO)9]2- (1), which was oxidized with [Cu(MeCN)4][BF4] to give the oxidation product [Se2Mn3(CO)9]- (2). Cluster 2 could be reconverted into cluster 1 by the addition of 4 M KOH/MeOH solutions in MeCN. While the trigonal-bipyramidal cluster 2 underwent cluster expansion to give rise to the large Se-inserted cluster [Se 6Mn6(CO)18]4- (3) upon the reaction with a 1/8 equiv of Se8 in KOH/MeOH solutions, the square-pyramidal cluster 1 was transformed into the even larger Se-rich cluster [Se 10Mn6(CO)18]4- (4) upon the addition of a 3/8 equiv of Se8 in MeOH. Cluster 3 underwent cluster expansion to form cluster 4 when treated with an additional 1/2 equiv of Se8 in MeCN. Conversely, cluster 4 was selectively reconverted into cluster 1 or 3 upon treatment with 4 or 2 equiv of Mn2(CO)10 in KOH/MeOH solutions, respectively. On the other hand, the Se6Mn6 cluster 3 was transformed into cluster 1 when treated with 2 equiv of Mn 2(CO)10 in KOH/MeOH solutions. Furthermore, when cluster 3 was treated with [Cu(MeCN)4][BF4] or Mn(CO) 5Br, cluster 2 and/or [Se5Mn4(CO) 12]2- (5) were obtained. X-ray analysis showed that cluster 5 consisted of four Mn(CO)3 fragments, which were further connected by one μ3-Se and two μ3- and μ4-Se2 moieties to give a nest-like cluster. Moreover, Se10Mn6 cluster 4 could also be transformed into cluster 5 upon reaction with [Cu(MeCN)4][BF4] or Mn(CO) 5Br. After a long reaction time, a new picnic-basket-like cluster, [Se4Mn3(CO)10]- (6), formed, which was also obtained from cluster 5 with [Cu(MeCN)4][BF4] or Mn(CO)5Br. Furthermore, the nature, cluster transformation and interconversion, and electrochemical properties of these Se-Mn-CO clusters were elucidated by molecular calculations at the B3PW91 level of the density functional theory.",

author = "Ho, {Chia Hua} and Chu, {Yen Yi} and Lin, {Chien Nan} and Chen, {Horng Wen} and Huang, {Chung Yi} and Minghuey Shieh",

year = "2010",

month = oct,

day = "11",

doi = "10.1021/om1006819",

language = "English",

volume = "29",

pages = "4396--4405",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "19",

}

TY - JOUR

T1 - Selenium-manganese carbonyl clusters

T2 - Synthesis, reversible transformation, electrochemical properties, and theoretical calculations

AU - Ho, Chia Hua

AU - Chu, Yen Yi

AU - Lin, Chien Nan

AU - Chen, Horng Wen

AU - Huang, Chung Yi

AU - Shieh, Minghuey

PY - 2010/10/11

Y1 - 2010/10/11

N2 - The reaction of Se8 with 6 equiv of Mn2(CO) 10 in concentrated KOH/MeOH solutions led to the formation of the odd-electron cluster [Se2Mn3(CO)9]2- (1), which was oxidized with [Cu(MeCN)4][BF4] to give the oxidation product [Se2Mn3(CO)9]- (2). Cluster 2 could be reconverted into cluster 1 by the addition of 4 M KOH/MeOH solutions in MeCN. While the trigonal-bipyramidal cluster 2 underwent cluster expansion to give rise to the large Se-inserted cluster [Se 6Mn6(CO)18]4- (3) upon the reaction with a 1/8 equiv of Se8 in KOH/MeOH solutions, the square-pyramidal cluster 1 was transformed into the even larger Se-rich cluster [Se 10Mn6(CO)18]4- (4) upon the addition of a 3/8 equiv of Se8 in MeOH. Cluster 3 underwent cluster expansion to form cluster 4 when treated with an additional 1/2 equiv of Se8 in MeCN. Conversely, cluster 4 was selectively reconverted into cluster 1 or 3 upon treatment with 4 or 2 equiv of Mn2(CO)10 in KOH/MeOH solutions, respectively. On the other hand, the Se6Mn6 cluster 3 was transformed into cluster 1 when treated with 2 equiv of Mn 2(CO)10 in KOH/MeOH solutions. Furthermore, when cluster 3 was treated with [Cu(MeCN)4][BF4] or Mn(CO) 5Br, cluster 2 and/or [Se5Mn4(CO) 12]2- (5) were obtained. X-ray analysis showed that cluster 5 consisted of four Mn(CO)3 fragments, which were further connected by one μ3-Se and two μ3- and μ4-Se2 moieties to give a nest-like cluster. Moreover, Se10Mn6 cluster 4 could also be transformed into cluster 5 upon reaction with [Cu(MeCN)4][BF4] or Mn(CO) 5Br. After a long reaction time, a new picnic-basket-like cluster, [Se4Mn3(CO)10]- (6), formed, which was also obtained from cluster 5 with [Cu(MeCN)4][BF4] or Mn(CO)5Br. Furthermore, the nature, cluster transformation and interconversion, and electrochemical properties of these Se-Mn-CO clusters were elucidated by molecular calculations at the B3PW91 level of the density functional theory.

AB - The reaction of Se8 with 6 equiv of Mn2(CO) 10 in concentrated KOH/MeOH solutions led to the formation of the odd-electron cluster [Se2Mn3(CO)9]2- (1), which was oxidized with [Cu(MeCN)4][BF4] to give the oxidation product [Se2Mn3(CO)9]- (2). Cluster 2 could be reconverted into cluster 1 by the addition of 4 M KOH/MeOH solutions in MeCN. While the trigonal-bipyramidal cluster 2 underwent cluster expansion to give rise to the large Se-inserted cluster [Se 6Mn6(CO)18]4- (3) upon the reaction with a 1/8 equiv of Se8 in KOH/MeOH solutions, the square-pyramidal cluster 1 was transformed into the even larger Se-rich cluster [Se 10Mn6(CO)18]4- (4) upon the addition of a 3/8 equiv of Se8 in MeOH. Cluster 3 underwent cluster expansion to form cluster 4 when treated with an additional 1/2 equiv of Se8 in MeCN. Conversely, cluster 4 was selectively reconverted into cluster 1 or 3 upon treatment with 4 or 2 equiv of Mn2(CO)10 in KOH/MeOH solutions, respectively. On the other hand, the Se6Mn6 cluster 3 was transformed into cluster 1 when treated with 2 equiv of Mn 2(CO)10 in KOH/MeOH solutions. Furthermore, when cluster 3 was treated with [Cu(MeCN)4][BF4] or Mn(CO) 5Br, cluster 2 and/or [Se5Mn4(CO) 12]2- (5) were obtained. X-ray analysis showed that cluster 5 consisted of four Mn(CO)3 fragments, which were further connected by one μ3-Se and two μ3- and μ4-Se2 moieties to give a nest-like cluster. Moreover, Se10Mn6 cluster 4 could also be transformed into cluster 5 upon reaction with [Cu(MeCN)4][BF4] or Mn(CO) 5Br. After a long reaction time, a new picnic-basket-like cluster, [Se4Mn3(CO)10]- (6), formed, which was also obtained from cluster 5 with [Cu(MeCN)4][BF4] or Mn(CO)5Br. Furthermore, the nature, cluster transformation and interconversion, and electrochemical properties of these Se-Mn-CO clusters were elucidated by molecular calculations at the B3PW91 level of the density functional theory.

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Selenium-manganese carbonyl clusters: Synthesis, reversible transformation, electrochemical properties, and theoretical calculations

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CCDC 835803: Experimental Crystal Structure Determination

CCDC 835802: Experimental Crystal Structure Determination

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Selenium-manganese carbonyl clusters: Synthesis, reversible transformation, electrochemical properties, and theoretical calculations

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CCDC 835803: Experimental Crystal Structure Determination

CCDC 835802: Experimental Crystal Structure Determination

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