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Synthesis, Characterization and Crystal Structures of Some Metal Carbonyl Linking Clusters of Osmium, Ruthenium and Cobalt Derived from Diethynylarenes

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Abstract

The use of various diethynylarene ligands in the synthesis of some metal carbonyl linking clusters is established. New dimeric complexes of osmium [{(μ-CO)Os3(CO)9}2(μ3-η2-diyne)], ruthenium [{(μ-H)Ru3(CO)9}2(μ3-η2,η2-diyne)] or [{(μ-CO)Ru3(CO)9}2(μ3-η2-diyne)] and cobalt [{Co2(CO)6}2(η2-diyne)] (diyne = HC≡CArC≡CH, Ar = 2,7-fluorene, 2,7-fluoren-9-one, bithiazole or bithiophene) have been prepared in good yields from the reaction of [Os3(CO)10(NCMe)2], [Ru3(CO)12] or [Ru3(CO)10(NCMe)2] and [Co2(CO)8] with half an equivalent of the appropriate diethynylarene ligand, respectively. All these cluster compounds have been characterized by IR and 1H NMR spectroscopies and mass spectrometry. The molecular structures of three of them have been determined by X-ray crystallography. For the group 8 osmium and ruthenium analogues, the hexanuclear carbonyl clusters consist of two trinuclear metal cores with the exhibition of the μ3-(η2-||) bonding mode for the acetylene groups when [M3(CO)10(NCMe)2] (M = Ru, Os) was used and the μ3-η2,η2 bonding mode when [Ru3(CO)12] served as the starting cluster. The tetracobalt species possesses two Co2C2 cores adopting the pseudo-tetrahedral geometry having the alkyne bond lying perpendicular to the Co–Co vector in each core. Density functional theory was also used to study the electronic structures of selected molecules.

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Acknowledgments

H. Li thanks the 111 Project and Beijing Engineering Research Center of Food Environment and Public Health from Minzu University of China (No. B08044 and No.10301-01404026) for financial support. Financial support from the National Natural Science Foundation of China (project number 51373145), Hong Kong Research Grants Council of HKSAR (HKBU203312) and Hong Kong Baptist University is gratefully acknowledged. The work was also supported by Partner State Key Laboratory of Environmental (SKLP-14-15-P011) and Biological Analysis and Strategic Development Fund of HKBU. Y. H. Lo gratefully acknowledges the financial support from the National Science Council of Taiwan (NSC 102-2113-M-845-001) and the project of the specific research fields in the University of Taipei, Taiwan. Dedicated to the Special Issue on 50 Years of Metal Cluster Chemistry.

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Authors and Affiliations

  1. College of Life and Environmental Sciences & Beijing Engineering Research Center of Food Environment and Public Health, Minzu University of China, Beijing, 100081, People’s Republic of China

    Hua Li

  2. Department of Chemistry, Partner State Key Laboratory of Environmental and Biological Analysis and Institute of Advanced Materials, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong, People’s Republic of China

    Fai-Lung Ting, Cheuk-Lam Ho, Hoi-Yan Lam, Nianyong Zhu & Wai-Yeung Wong

  3. Department of Applied Physics and Chemistry, University of Taipei, Taipei, 100, Taiwan

    Yih Hsing Lo

  4. HKBU Institute of Research and Continuing Education, Shenzhen Virtual University Park, Shenzhen, 518057, People’s Republic of China

    Wai-Yeung Wong

  5. Department of Chemistry, The Hong Kong University of Science and Technology, Clearwater Bay, Hong Kong, People’s Republic of China

    Man-Sing Cheung & Zhenyang Lin

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Li, H., Ting, FL., Ho, CL. et al. Synthesis, Characterization and Crystal Structures of Some Metal Carbonyl Linking Clusters of Osmium, Ruthenium and Cobalt Derived from Diethynylarenes. J Clust Sci 26, 291–307 (2015). https://doi.org/10.1007/s10876-014-0785-2

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