Revisiting the Synthesis and Nucleophilic Reactivity of an Anionic Copper Superoxide Complex

Wilson Bailey
,
Nicole L. Gagnon
,
Courtney E. Elwell
,
Anna C. Cramblitt
,
Caitlin J. Bouchey
,
William B. Tolman

Washington University in St. Louis
,
University of Minnesota

Research Output:

Contribution to journal

Article

Peer-review

Abstract

The addition of 1 equiv of KO2 and Kryptofix222 (Krypt) in CH3CN to a solution of LCu(CH3CN) [L = N,N′-bis(2,6-diisopropylphenyl)-2,6-pyridinecarboxamide] in tetrahydrofuran at −80 °C yielded [K(Krypt)][LCuO2], the enhanced stability of which enabled reexamination of its reactivity with 2-phenylpropionaldehyde (2-PPA). Mechanistic and product analysis studies revealed that [K(Krypt)][LCuO2] reacts with wet 2-PPA to form [LCuOH]−, which then deprotonates 2-PPA to yield the copper(II) enolate complex [LCu(OC═C(Me)Ph)]−. Acetophenone was observed upon workup of this complex or mixtures of KO2 and 2-PPA alone, in support of an alternative mechanism(s) to the one proposed previously involving an initial nucleophilic attack at the carbonyl group of 2-PPA.

Bibliographic Information

Output type

Research Output:

Contribution to journal

Article

Peer-review

Original language

American English

Pages from-to (Number of pages)

Pages 4706 (4711 pages)

Journal (Volume, Issue Number)

Inorganic Chemistry (Volume 58, Issue 8)

Publication milestones

Published - 22/03/2019

Publication status

Published - 22/03/2019

ISSN

0020-1669

Publication IDs

Scopus: 85063405389