Coordination of a Diphosphine-Ketone Ligand to Ni(0), Ni(I), and Ni(II): Reduction-Induced Coordination
Publication date
2015-06-22
Authors
Saes, Bart W. H.
Verhoeven, D.G.A.
Lutz, Martin
Klein Gebbink, R.J.M.
Moret, Marc Etienne
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Supervisors
Document Type
Article
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taverne
Abstract
The coordination chemistry of the diphosphine-ketone ligand 2,2′-bis(diphenylphosphino)benzophenone (<sup>Ph</sup>dpbp) with nickel is reported. The ketone moiety does not bind to Ni(II) in the complex (<sup>Ph</sup>dpbp)NiCl<inf>2</inf>, whereas reduction to Ni(I) or Ni(0) induces η<sup>2</sup>(C,O) coordination of the ketone to form the pseudotetrahedral complexes (<sup>Ph</sup>dpbp)NiCl and (<sup>Ph</sup>dpbp)Ni(PPh<inf>3</inf>). DFT calculations indicate that the metal-ketone bond is dominated by π back-donation; hence, <sup>Ph</sup>dpbp functions as a hemilabile acceptor ligand in this series of complexes. (Chemical Equation Presented).
Keywords
Taverne, Organic Chemistry, Physical and Theoretical Chemistry, Inorganic Chemistry
Citation
Saes, B W H, Verhoeven, D G A, Lutz, M, Klein Gebbink, R J M & Moret, M E 2015, 'Coordination of a Diphosphine-Ketone Ligand to Ni(0), Ni(I), and Ni(II) : Reduction-Induced Coordination', Organometallics, vol. 34, no. 12, pp. 2710-2713. https://doi.org/10.1021/acs.organomet.5b00264