Lewis acid-promoted oxidative addition at a [Ni0(diphosphine)2] complex: the critical role of a secondary coordination sphere

Joseph A. Zurakowski, Brady J. H. Austen, Maeve C. Dufour, Denis M. Spasyuk, David J. Nelson, Marcus W. Drover

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10 Citations (Scopus)
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Oxidative addition represents a critical elementary step in myriad catalytic transformations. Here, the importance of thoughtful ligand design cannot be overstated. In this work, we report the intermolecular activation of iodobenzene (PhI) at a coordinatively saturated 18-electron [Ni 0(diphosphine) 2] complex bearing a Lewis acidic secondary coordination sphere. Whereas alkyl-substituted diphosphine complexes of Group 10 are known to be unreactive in such reactions, we show that [Ni 0(P 2B Cy 4) 2] (P 2B Cy 4=1,2-bis(di(3-dicyclohexylboraneyl)-propylphosphino)ethane) is competent for room-temperature PhI cleavage to give [Ni II(P 2B Cy 4)(Ph)(I)]. This difference in oxidative addition reactivity has been scrutinized computationally – an outcome that is borne out in ring-opening to provide the reactive precursor – for [Ni 0(P 2B Cy 4) 2], a “boron-trapped” 16-electron κ 1-diphosphine Ni(0) complex. Moreover, formation of [Ni II(P 2B Cy 4)(Ph)(I)] is inherent to the P 2B Cy 4 secondary coordination sphere: treatment of the Lewis adduct, [Ni 0(P 2B Cy 4) 2(DMAP) 8] with PhI provides [Ni II(P 2B Cy 4) 2(DMAP) 8(I)]I via iodine-atom abstraction and not a [Ni II(Ph)(I)(diphosphine)] compound – an unusual secondary sphere effect. Finally, the reactivity of [Ni 0(P 2B Cy 4) 2] with 4-iodopyridine was surveyed, which resulted in a pyridyl-borane linked oligomer. The implications of these outcomes are discussed in the context of designing strongly donating, and yet labile diphosphine ligands for use in a critical bond activation step relevant to catalysis.

Original languageEnglish
Pages (from-to)16021-16027
Number of pages7
JournalChemistry - A European Journal
Issue number64
Early online date12 Oct 2021
Publication statusPublished - 17 Nov 2021


  • boron
  • metal-ligand cooperativity
  • cross-coupling
  • nickel
  • diphosphine ligand


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