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Group 10 Metal Dithiolene Bis(isonitrile) Complexes: Synthesis, Structures, Properties, and Reactivity

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    Group 10 Metal Dithiolene Bis(isonitrile) Complexes: Synthesis, Structures, Properties, and Reactivity
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    Organometallics

    Cite this: Organometallics 2020, 39, 15, 2854–2870
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    https://doi.org/10.1021/acs.organomet.0c00375
    Published July 30, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    The reaction of [(Ph2C2S2)2M] (M = Ni2+, Pd2+, Pt2+) with 2 equiv of RN≡C (R = Me (a), Bn (b), Cy (c), tBu (d), 1-Ad (e), Ph (f)) yields [(Ph2C2S2)M(C≡NR)2] (M = Ni2+, 4a–f; M = Pd2+, 5a–f; M = Pt2+, 6a–f), which are air-stable and amenable to chromatographic purification. All members have been characterized crystallographically. Structurally, progressively greater planarity tends to be manifested as M varies from Ni to Pt, and a modest decrease in the C≡N bond length of coordinated C≡NR appears in moving from Ni toward Pt. Vibrational spectroscopy (CH2Cl2 solution) reveals νC≡N frequencies for [(Ph2C2S2)M(C≡NR)2] that are substantially higher than those for free C≡NR and increase as M ranges from Ni to Pt. This trend is interpreted as arising from an increasingly positive charge at M that stabilizes the linear, charge-separated resonance form of the ligand over the bent form with lowered C–N bond order. UV–vis spectra reveal lowest energy transitions that are assigned as HOMO (dithiolene π) → LUMO (M–L σ*) excitations. One-electron oxidations of [(Ph2C2S2)M(C≡NR)2] are observed at ∼+0.5 V due to Ph2C2S22– → Ph2C2S–S• + e–. Chemical oxidation of [(Ph2C2S2)Pt(C≡NtBu)2] with [(Br-p-C6H4)3N][SbCl6] yields [(Ph2C2S–S•)Pt(C≡NtBu)2]+, identified spectroscopically, but in the crystalline state [[(Ph2C2S–S•)Pt(C≡NtBu)2]2]2+ prevails, which forms via axial Pt···S interactions and pyramidalization at the metal. Complete substitution of MeNC from [(Ph2C2S2)Ni(C≡NMe)2] by 2,6-Me2py under forcing conditions yields [(2,6-Me2py)Ni(μ2-η1,η1-S′,η1-S″-S2C2Ph2)]2 (8), which features a folded Ni2S2 core. In most cases, isocyanide substitution from [(Ph2C2S2)M(C≡NMe)2] with monodentate ligands (L = phosphine, CN–, carbene) leads to [(Ph2C2S2)M(L)(C≡NMe)]n (n = 0, 1−), wherein νC≡N varies according to the relative σ-donating power of L (9–21). The use of 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) provides [(Ph2C2S2)M(IPr)(C≡NMe)] for M = Ni (18), Pd (19), but for Pt, attack by IPr at the isocyanide carbon occurs to yield the unusual η1,κC-ketenimine complex [(Ph2C2S2)Pt(C(NMe)(IPr))(C≡NMe)] (20).

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.organomet.0c00375.

    • Procedures for crystal growth, X-ray diffraction data collection, and structure solution and refinement, summary of unit cell and refinement data, thermal ellipsoid plots with complete atom labeling, spectroscopic, electrochemical, and analytical data for the compounds reported, and description of computation procedures (PDF)

    • Coordinates for geometry optimized structures (XYZ)

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    CCDC 1920776–1920790 and 1995894–1995907 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    This article is cited by 8 publications.

    1. Manuel Quiroz, Marcetta Y. Darensbourg. Development of (NO)Fe(N2S2) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach. Accounts of Chemical Research 2024, 57 (6) , 831-844. https://doi.org/10.1021/acs.accounts.3c00667
    2. Che Wu, Lakshmi Nishanth Kakarla, Chandru P. Chandrasekaran, Xiaodong Zhang, Joel T. Mague, Stephen Sproules, James P. Donahue. Asymmetric by Design: Heteroleptic Coordination Compounds with Redox-Active Dithiolene and 1,2,4,5-Tetrakis(isopropylthio)benzene Ligands. Inorganic Chemistry 2024, 63 (1) , 173-183. https://doi.org/10.1021/acs.inorgchem.3c02928
    3. Ayan Das, Tuhin Ganguly, Amit Majumdar. Thiolate Coordination vs C–S Bond Cleavage of Thiolates in Dinickel(II) Complexes. Inorganic Chemistry 2021, 60 (2) , 944-958. https://doi.org/10.1021/acs.inorgchem.0c03068
    4. V. V. Sharutin, E. S. Mekhanoshina. Platinum Nitrile Complexes. Synthesis and Structure. Reviews and Advances in Chemistry 2023, 13 (3) , 206-237. https://doi.org/10.1134/S2634827623600172
    5. Victor V. Verpekin, Oleg S. Chudin, Alexander A. Kondrasenko, Galina V. Burmakina, Alexander D. Vasiliev, Dmitry V. Zimonin, Anatoly I. Rubaylo. Chemistry of vinylidene complexes—XXVII—new µ-vinylidene MnPt complexes with platinum-coordinated 1-adamantyl isocyanide ligand: spectroscopic, structural and electrochemical study. Transition Metal Chemistry 2022, 47 (7-8) , 283-292. https://doi.org/10.1007/s11243-022-00511-w
    6. Manuel Quiroz, Molly M. Lockart, Mohamed R. Saber, Shaik Waseem Vali, Lindy C. Elrod, Brad S. Pierce, Michael B. Hall, Marcetta Y. Darensbourg. Cooperative redox and spin activity from three redox congeners of sulfur-bridged iron nitrosyl and nickel dithiolene complexes. Proceedings of the National Academy of Sciences 2022, 119 (25) https://doi.org/10.1073/pnas.2201240119
    7. Nabhendu Pal, Tilak Naskar, Amit Majumdar. Synthesis, structural diversity and redox reactions in 1, 2- Bis(diphenylphopshinoethane)Nickel(II)-Thiolate complexes. Inorganica Chimica Acta 2022, 531 , 120738. https://doi.org/10.1016/j.ica.2021.120738
    8. Jayaraman Selvakumar, Scott M. Simpson, Eva Zurek, Kuppuswamy Arumugam. An electrochemically controlled release of NHCs using iron bis(dithiolene) N-heterocyclic carbene complexes. Inorganic Chemistry Frontiers 2021, 8 (1) , 59-71. https://doi.org/10.1039/D0QI00638F
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    Organometallics

    Cite this: Organometallics 2020, 39, 15, 2854–2870
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.0c00375
    Published July 30, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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