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New Tri- and Pentanuclear Osmium Clusters from [Os3(CO)10(NCMe)2] and Pyrrolidine: Reactivity and X-ray Structure of [HOs3(CO)9(µ,κ2-N=C(CH3)C=NCH2CH2CH2)] and [H3Os5(CO)14(µ,η1,κ1-N=CCH2CH2CH2)]

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Abstract

[Os3(CO)10(NCMe)2] reacts with pyrrolidine in refluxing benzene to give the known clusters [HOs3(CO)10(µ,κ1-NCH2CH2CH2CH2)] (1) and [HOs3(CO)10(µ,η1,κ1-C=NCH2CH2CH2)] (2), in addition to the new triosmium cluster [HOs3(CO)9(µ,κ2-N=C(CH3)C=NCH2CH2CH2)] (5), whose ancillary heterocyclic ligand is formed by C–C coupling involving the nitrile carbon of NCCH3 and the α-carbon of pyrrolidine. Refluxing 2 in n-octane furnishes the known µ3-imidoyl cluster [HOs3(CO)9(µ3,η1,κ1-C=NCH2CH2CH2)] (4) along with the new pentaosmium cluster [H3Os5(CO)14(µ,η1,κ1-C=NCH2CH2CH2)] (6) which exhibits a metallic core based on an edge-bridged tetrahedron. The doubly metalated pyrrolidine ligand ligates one of the apical osmium atoms in the Os4 tetrahedron and the bridging Os(CO)3 moiety in 6. The bonding in clusters 5 and 6 has been investigated by electronic structure calculations.

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Acknowledgements

Financial support from the Ministry of Education, the Government of the People’s Republic of Bangladesh (SG and SEK) and the Robert A. Welch Foundation (Grant B-1093-MGR) is acknowledged. The DFT calculations were performed at UNT through CASCaM, which is an NSF-supported facility (CHE-1531468).

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Authors and Affiliations

  1. Department of Chemistry, Jahangirnagar University, Savar, Dhaka, 1342, Bangladesh

    Shahin A. Begum, Mst. Asha Aktar, Israt Jahan, Shishir Ghosh & Shariff E. Kabir

  2. Department of Chemistry, University of North Texas, Denton, TX, 76203, USA

    Vladimir N. Nesterov & Michael G. Richmond

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  1. Shahin A. Begum
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10876_2022_2305_MOESM1_ESM.docx

Supplementary file1 (DOCX 2513 kb) Contour plots of the HOMO and LUMO for clusters 5 (A) and 6 (B) (Figure S1). Atomic coordinates and energies for all DFT-optimized structures are available upon request (MGR)

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Begum, S.A., Aktar, M.A., Jahan, I. et al. New Tri- and Pentanuclear Osmium Clusters from [Os3(CO)10(NCMe)2] and Pyrrolidine: Reactivity and X-ray Structure of [HOs3(CO)9(µ,κ2-N=C(CH3)C=NCH2CH2CH2)] and [H3Os5(CO)14(µ,η1,κ1-N=CCH2CH2CH2)]. J Clust Sci 34, 1391–1399 (2023). https://doi.org/10.1007/s10876-022-02305-7

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