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Synthesis, Coordination Chemistry, and Mechanistic Studies of P,N-Type Phosphaalkene-Based Rh(I) Complexes

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    Synthesis, Coordination Chemistry, and Mechanistic Studies of P,N-Type Phosphaalkene-Based Rh(I) Complexes
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2022, 61, 30, 11639–11650
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    https://doi.org/10.1021/acs.inorgchem.2c01158
    Published July 20, 2022
    Copyright © 2022 The Authors. Published by American Chemical Society
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    Abstract

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    The synthesis of P,N-phosphaalkene ligands, py-CH═PMes* (1, py = 2-pyridyl, Mes* = 2,4,6-tBu–C6H2) and the novel quin-CH═PMes* (2, quin = 2-quinolinyl) is described. The reaction with [Rh(μ-Cl)cod]2 produces Rh(I) bis(phosphaalkene) chlorido complexes 3 and 4 with distorted trigonal bipyramidal coordination environments. Complexes 3 and 4 show a pronounced metal-to-ligand charge transfer (MLCT) from Rh into the ligand P═C π* orbitals. Upon heating, quinoline-based complex 4 undergoes twofold C–H bond activation at the o-tBu groups of the Mes* substituents to yield the cationic bis(phosphaindane) Rh(I) complex 5, which could not be observed for the pyridine-based analogue 3. Using sub- or superstoichiometric amounts of AgOTf the C–H bond activation at an o-tBu group of one or at both Mes* was detected, respectively. Density functional theory (DFT) studies suggest an oxidative proton shift pathway as an alternative to a previously reported high-barrier oxidative addition at Rh(I). The Rh(I) mono- and bis(phosphaindane) triflate complexes 6 and 7, respectively, undergo deprotonation at the benzylic CH2 group of the phosphaindane unit in the presence of KOtBu to furnish neutral, distorted square-planar Rh(I) complexes 8 and 9, respectively, with one of the P,N ligands being dearomatized. All complexes were fully characterized, including multinuclear NMR, vibrational, and ultraviolet–visible (UV–vis) spectroscopy, as well as single-crystal X-ray and elemental analysis.

    Copyright © 2022 The Authors. Published by American Chemical Society

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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.inorgchem.2c01158.

    • General information; experimental methods; NMR spectra; electrochemical studies; computational details; and X-ray crystallographic data (PDF)

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    CCDC 2162622–2162626 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 10 publications.

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    2. Iulia-Andreea Aghion, Raluca Septelean, Alex-Cristian Tomut, Ionut-Tudor Moraru, Albert Soran, Gabriela Nemes. Coordination Ability of Phosphavinyl(oxo and thioxo)phosphoranes (P═C–P═X; X = O, S) toward Transition Metals. Organometallics 2024, 43 (18) , 2062-2076. https://doi.org/10.1021/acs.organomet.4c00270
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    6. Kushik, A. Petrov, D. Ranieri, L. Edelmann, T. Beweries, C. Hering‐Junghans. The Azide‐Wittig Reaction. Angewandte Chemie International Edition 2024, 63 (50) https://doi.org/10.1002/anie.202412982
    7. Christian Hering‐Junghans. Phosphinidentransfer und P‐Al‐Mehrfachbindungen. Nachrichten aus der Chemie 2024, 72 (11) , 59-61. https://doi.org/10.1002/nadc.20244145308
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    9. Henry T. G. Walsgrove, Khadiza (Rodella) K. Chowdhury, Philipp Dabringhaus, Brian O. Patrick, Derek P. Gates. Palladium(II) Complexes of 1‐Phosphaisoprene Molecules and Polymers: Reversible Cross‐Linking of a Phosphorus‐Containing Polymer. European Journal of Inorganic Chemistry 2023, 26 (20) https://doi.org/10.1002/ejic.202300182
    10. Priyanka Gupta, Hans-Joachim Drexler, Richard Wingad, Duncan Wass, Eszter Baráth, Torsten Beweries, Christian Hering-Junghans. P,N-type phosphaalkene-based Ir( i ) complexes: synthesis, coordination chemistry, and catalytic applications. Inorganic Chemistry Frontiers 2023, 10 (8) , 2285-2293. https://doi.org/10.1039/D3QI00142C
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2022, 61, 30, 11639–11650
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.2c01158
    Published July 20, 2022
    Copyright © 2022 The Authors. Published by American Chemical Society
    Request reuse permissions

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