Acetylacetonate and Acetate Complexes of Nickel(II) Catalyse the Air Oxidation of Phosphines

Line Sofie Hansen, Vibe Boel Jakobsen, Vickie McKee, Christine J. McKenzie*

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The polymeric complex trans-[Ni(acac)22-dppe)]n·2MeCN {1a, dppe = 1,2-ethylenebis(diphenylphosphine)} is sometimes transiently deposited from the reaction of [Ni(acac)2] with dppe in MeCN prior to its facile onwards air oxidation to final crystallization of a doubly-oxygenated relative, cis-[Ni(acac)22-dppeO2)]n {2, dppeO2 = 1,2-ethylenebis(diphenylphosphineoxide)}. A similar unsolvated phase of the initial polymer, trans-[Ni(acac)22-dppe)]n (1b), can be isolated from toluene. The oxidation of dppe by O2 is catalytic and dppeO2 was isolated in close to stoichiometric yields from solutions containing 5 % Ni(acac)2 relative to dppe. The reaction rate slows after a few turnovers due to inhibition by the product. The relative yields of dppeO2 are higher than those from catalytic air oxidation of methyldiphenylphosphine and triphenylphosphine and we speculate that a pathway for this reaction involves a dimetallic cooperativity enabled specifically by dppe.

TidsskriftEuropean Journal of Inorganic Chemistry
Udgave nummer44
Sider (fra-til)4163-4169
StatusUdgivet - 30. nov. 2020

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