Trigonal-Bipyramidal and Square-Pyramidal Chromium[BOND]Manganese Chalcogenide Clusters, [E2CrMn2(CO)n]2− (E=S, Se, Te; n=9, 10): Synthesis, Electrochemistry, UV/Vis Absorption, and Computational Studies

Authors

  • Prof. Dr. Minghuey Shieh,

    Corresponding author
    1. Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan (Republic of China), Fax: : (+886) 2-2930-9081
    • Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan (Republic of China), Fax: : (+886) 2-2930-9081

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  • Chun-Hsien Yu,

    1. Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan (Republic of China), Fax: : (+886) 2-2930-9081
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  • Yen-Yi Chu,

    1. Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan (Republic of China), Fax: : (+886) 2-2930-9081
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  • Yu-Wen Guo,

    1. Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan (Republic of China), Fax: : (+886) 2-2930-9081
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  • Chung-Yi Huang,

    1. Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan (Republic of China), Fax: : (+886) 2-2930-9081
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  • Kai-Jieah Hsing,

    1. Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan (Republic of China), Fax: : (+886) 2-2930-9081
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  • Pei-Chi Chen,

    1. Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan (Republic of China), Fax: : (+886) 2-2930-9081
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  • Chung-Feng Lee

    1. Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan (Republic of China), Fax: : (+886) 2-2930-9081
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Abstract

The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr[BOND]Mn[BOND]carbonyl clusters, [E2CrMn2(CO)9]2− (E=S, ; Se, ). Clusters and were isostructural with one another and each displayed a trigonal-bipyramidal structure, with the CrMn2 triangle axially capped by two μ3-E atoms. The analogous telluride cluster, [Te2CrMn2(CO)9]2− (), was obtained from the ring-closure of Te2Mn2 ring complex [Te2Mn2Cr2(CO)18]2− (). Upon bubbling with CO, clusters and were readily converted into square-pyramidal clusters, [E2CrMn2(CO)10]2− (E=Se, ; Te, ), accompanied with the cleavage of one Cr[BOND]Mn bond. According to SQUID analysis, cluster was paramagnetic, with S=1 at room temperature; however, the Se analogue () was spectroscopically proposed to be diamagnetic, as verified by TD-DFT calculations. Cluster could be further carbonylated, with cleavage of the Mn[BOND]Mn bond to produce a new arachno-cluster, [Te2CrMn2(CO)11]2− (). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations.

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