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

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

doi:10.1002/ejic.202000663

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

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

^*Corresponding author for this work

Department of Physics, Chemistry and Pharmacy

Research output: Contribution to journal › Journal article › Research › peer-review

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Abstract

The polymeric complex trans-[Ni(acac)₂(µ₂-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)₂(µ₂-dppeO₂)]_n {2, dppeO₂ = 1,2-ethylenebis(diphenylphosphineoxide)}. A similar unsolvated phase of the initial polymer, trans-[Ni(acac)₂(µ₂-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.

Original language	English
Journal	European Journal of Inorganic Chemistry
Volume	2020
Issue number	44
Pages (from-to)	4163-4169
ISSN	1434-1948
DOIs	https://doi.org/10.1002/ejic.202000663
Publication status	Published - 30. Nov 2020

Keywords

Acetate
Nickel
Oxygen activation
Phosphine oxidation
β-Diketonate

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10.1002/ejic.202000663

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title = "Acetylacetonate and Acetate Complexes of Nickel(II) Catalyse the Air Oxidation of Phosphines",

abstract = "The polymeric complex trans-[Ni(acac)2(µ2-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)2(µ2-dppeO2)]n {2, dppeO2 = 1,2-ethylenebis(diphenylphosphineoxide)}. A similar unsolvated phase of the initial polymer, trans-[Ni(acac)2(µ2-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.",

keywords = "Acetate, Nickel, Oxygen activation, Phosphine oxidation, β-Diketonate",

author = "Hansen, {Line Sofie} and Jakobsen, {Vibe Boel} and Vickie McKee and McKenzie, {Christine J.}",

year = "2020",

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doi = "10.1002/ejic.202000663",

language = "English",

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TY - JOUR

T1 - Acetylacetonate and Acetate Complexes of Nickel(II) Catalyse the Air Oxidation of Phosphines

AU - Hansen, Line Sofie

AU - Jakobsen, Vibe Boel

AU - McKee, Vickie

AU - McKenzie, Christine J.

PY - 2020/11/30

Y1 - 2020/11/30

N2 - The polymeric complex trans-[Ni(acac)2(µ2-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)2(µ2-dppeO2)]n {2, dppeO2 = 1,2-ethylenebis(diphenylphosphineoxide)}. A similar unsolvated phase of the initial polymer, trans-[Ni(acac)2(µ2-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.

AB - The polymeric complex trans-[Ni(acac)2(µ2-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)2(µ2-dppeO2)]n {2, dppeO2 = 1,2-ethylenebis(diphenylphosphineoxide)}. A similar unsolvated phase of the initial polymer, trans-[Ni(acac)2(µ2-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.

KW - Acetate

KW - Nickel

KW - Oxygen activation

KW - Phosphine oxidation

KW - β-Diketonate

U2 - 10.1002/ejic.202000663

DO - 10.1002/ejic.202000663

M3 - Journal article

AN - SCOPUS:85092095005

SN - 1434-1948

VL - 2020

SP - 4163

EP - 4169

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 44

ER -

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

Abstract

Keywords

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