Syntheses and X-ray Structures of a Series of Chalcogen-Containing Manganese Carbonylates [E2Mn3(CO)9]-, [E8C2Mn2(CO)6]2-, and [E2Mn4(CO)12]2- (E = Se, S)

Kuo Chih Huang; Yi Chou Tsai; Gene Hsiang Lee; Shie Ming Peng; Minghuey Shieh

doi:10.1021/ic961482b

Syntheses and X-ray Structures of a Series of Chalcogen-Containing Manganese Carbonylates [E₂Mn₃(CO)₉]^-, [E₈C₂Mn₂(CO)₆]^2-, and [E₂Mn₄(CO)₁₂]^2- (E = Se, S)

Kuo Chih Huang^*, Yi Chou Tsai, Gene Hsiang Lee, Shie Ming Peng, Minghuey Shieh

^*Corresponding author for this work

Department of Chemistry

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Abstract

The reaction of SeO₂ with Mn₂(CO)₁₀/KOH in methanol solution forms a trigonal bipyramid cluster anion [Se₂Mn₃(CO)₉]^- (Ia). Cluster la can also be synthesized from the treatment of Se powder with Mn₂(CO)₁₀/KOH in 2:1 molar ratio in methanol solution. If Se is reacted with Mn₂(CO)₁₀/KOH in a molar ratio of 8:1, the deoxygenation occurs to produce a novel cluster [Se₈C₂Mn₂(CO)₆]^2- (IIa). Cluster IIa can readily transform into a new octahedral cluster [Se₈C₂Mn₄(CO)₁₂]^2- (IIIa) by further treatment with Mn₂(CO)₁₀/KOH in CH₂C1₂/ MeOH solutions, and the use of a molar ratio of 1:1 of Se powder to Mn₂(CO)₁₀/KOH in methanol also can yield complex IIIa. In the sulfur-manganese system, the synthesis of the analogous complexes [S₂Mn₃(CO)₉]^- (Ib), [S₈C₂Mn₂(CO)₆]^2- (IIb), and [S₂Mn₄(CO)₁₂]^2- (IIIb) also can be accomplished from the reactions of S powder with Mn₂(CO)₁₀/KOH in similar fashions. Clusters Ia-IIIa and Ib-IIIb are fully characterized by spectroscopic methods or/and X-ray analyses. The novel clusters [E₈C₂Mn₂(CO)₆]^2- (E = Se, IIa; E = S, IIb) each consist of two separate Mn(CO)₃ groups which are doubly bridged by two CE₄ fragments. Clusters Ia and Ib each display a trigonal bipyramid framework with two chalcogen atoms in the axial positions, while clusters IIIa and IIIb each exhibit an octahedral metal skeleton.

Original language	English
Pages (from-to)	4421-4425
Number of pages	5
Journal	Inorganic Chemistry
Volume	36
Issue number	20
DOIs	https://doi.org/10.1021/ic961482b
Publication status	Published - 1997

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{d0071fa312c44e3e831bd28b8112af7b,

title = "Syntheses and X-ray Structures of a Series of Chalcogen-Containing Manganese Carbonylates [E2Mn3(CO)9]-, [E8C2Mn2(CO)6]2-, and [E2Mn4(CO)12]2- (E = Se, S)",

abstract = "The reaction of SeO2 with Mn2(CO)10/KOH in methanol solution forms a trigonal bipyramid cluster anion [Se2Mn3(CO)9]- (Ia). Cluster la can also be synthesized from the treatment of Se powder with Mn2(CO)10/KOH in 2:1 molar ratio in methanol solution. If Se is reacted with Mn2(CO)10/KOH in a molar ratio of 8:1, the deoxygenation occurs to produce a novel cluster [Se8C2Mn2(CO)6]2- (IIa). Cluster IIa can readily transform into a new octahedral cluster [Se8C2Mn4(CO)12]2- (IIIa) by further treatment with Mn2(CO)10/KOH in CH2C12/ MeOH solutions, and the use of a molar ratio of 1:1 of Se powder to Mn2(CO)10/KOH in methanol also can yield complex IIIa. In the sulfur-manganese system, the synthesis of the analogous complexes [S2Mn3(CO)9]- (Ib), [S8C2Mn2(CO)6]2- (IIb), and [S2Mn4(CO)12]2- (IIIb) also can be accomplished from the reactions of S powder with Mn2(CO)10/KOH in similar fashions. Clusters Ia-IIIa and Ib-IIIb are fully characterized by spectroscopic methods or/and X-ray analyses. The novel clusters [E8C2Mn2(CO)6]2- (E = Se, IIa; E = S, IIb) each consist of two separate Mn(CO)3 groups which are doubly bridged by two CE4 fragments. Clusters Ia and Ib each display a trigonal bipyramid framework with two chalcogen atoms in the axial positions, while clusters IIIa and IIIb each exhibit an octahedral metal skeleton.",

author = "Huang, {Kuo Chih} and Tsai, {Yi Chou} and Lee, {Gene Hsiang} and Peng, {Shie Ming} and Minghuey Shieh",

year = "1997",

doi = "10.1021/ic961482b",

language = "English",

volume = "36",

pages = "4421--4425",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

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T1 - Syntheses and X-ray Structures of a Series of Chalcogen-Containing Manganese Carbonylates [E2Mn3(CO)9]-, [E8C2Mn2(CO)6]2-, and [E2Mn4(CO)12]2- (E = Se, S)

AU - Huang, Kuo Chih

AU - Tsai, Yi Chou

AU - Lee, Gene Hsiang

AU - Peng, Shie Ming

AU - Shieh, Minghuey

PY - 1997

Y1 - 1997

N2 - The reaction of SeO2 with Mn2(CO)10/KOH in methanol solution forms a trigonal bipyramid cluster anion [Se2Mn3(CO)9]- (Ia). Cluster la can also be synthesized from the treatment of Se powder with Mn2(CO)10/KOH in 2:1 molar ratio in methanol solution. If Se is reacted with Mn2(CO)10/KOH in a molar ratio of 8:1, the deoxygenation occurs to produce a novel cluster [Se8C2Mn2(CO)6]2- (IIa). Cluster IIa can readily transform into a new octahedral cluster [Se8C2Mn4(CO)12]2- (IIIa) by further treatment with Mn2(CO)10/KOH in CH2C12/ MeOH solutions, and the use of a molar ratio of 1:1 of Se powder to Mn2(CO)10/KOH in methanol also can yield complex IIIa. In the sulfur-manganese system, the synthesis of the analogous complexes [S2Mn3(CO)9]- (Ib), [S8C2Mn2(CO)6]2- (IIb), and [S2Mn4(CO)12]2- (IIIb) also can be accomplished from the reactions of S powder with Mn2(CO)10/KOH in similar fashions. Clusters Ia-IIIa and Ib-IIIb are fully characterized by spectroscopic methods or/and X-ray analyses. The novel clusters [E8C2Mn2(CO)6]2- (E = Se, IIa; E = S, IIb) each consist of two separate Mn(CO)3 groups which are doubly bridged by two CE4 fragments. Clusters Ia and Ib each display a trigonal bipyramid framework with two chalcogen atoms in the axial positions, while clusters IIIa and IIIb each exhibit an octahedral metal skeleton.

AB - The reaction of SeO2 with Mn2(CO)10/KOH in methanol solution forms a trigonal bipyramid cluster anion [Se2Mn3(CO)9]- (Ia). Cluster la can also be synthesized from the treatment of Se powder with Mn2(CO)10/KOH in 2:1 molar ratio in methanol solution. If Se is reacted with Mn2(CO)10/KOH in a molar ratio of 8:1, the deoxygenation occurs to produce a novel cluster [Se8C2Mn2(CO)6]2- (IIa). Cluster IIa can readily transform into a new octahedral cluster [Se8C2Mn4(CO)12]2- (IIIa) by further treatment with Mn2(CO)10/KOH in CH2C12/ MeOH solutions, and the use of a molar ratio of 1:1 of Se powder to Mn2(CO)10/KOH in methanol also can yield complex IIIa. In the sulfur-manganese system, the synthesis of the analogous complexes [S2Mn3(CO)9]- (Ib), [S8C2Mn2(CO)6]2- (IIb), and [S2Mn4(CO)12]2- (IIIb) also can be accomplished from the reactions of S powder with Mn2(CO)10/KOH in similar fashions. Clusters Ia-IIIa and Ib-IIIb are fully characterized by spectroscopic methods or/and X-ray analyses. The novel clusters [E8C2Mn2(CO)6]2- (E = Se, IIa; E = S, IIb) each consist of two separate Mn(CO)3 groups which are doubly bridged by two CE4 fragments. Clusters Ia and Ib each display a trigonal bipyramid framework with two chalcogen atoms in the axial positions, while clusters IIIa and IIIb each exhibit an octahedral metal skeleton.

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Syntheses and X-ray Structures of a Series of Chalcogen-Containing Manganese Carbonylates [E₂Mn₃(CO)₉]^-, [E₈C₂Mn₂(CO)₆]^2-, and [E₂Mn₄(CO)₁₂]^2- (E = Se, S)

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