Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity

Journal of the American Chemical Society
Amanda R CorcosJohn F Berry

Abstract

Bimetallic (Et4N)2[Co2(L)2], (Et4N)2[1] (where (L)(3-) = (N(o-PhNC(O)(i)Pr)2)(3-)) reacts with 2 equiv of O2 to form the monometallic species (Et4N)[Co(L)O2], (Et4N)[3]. A crystallographically characterized analog (Et4N)2[Co(L)CN], (Et4N)2[2], gives insight into the structure of [3](1-). Magnetic measurements indicate [2](2-) to be an unusual high-spin Co(II)-cyano species (S = 3/2), while IR, EXAFS, and EPR spectroscopies indicate [3](1-) to be an end-on superoxide complex with an S = 1/2 ground state. By X-ray spectroscopy and calculations, [3](1-) features a high-spin Co(II) center; the net S = 1/2 spin state arises after the Co electrons couple to both the O2(•-) and the aminyl radical on redox non-innocent (L(•))(2-). Dianion [1](2-) shows both nucleophilic and electrophilic catalytic reactivity upon activation of O2 due to the presence of both a high-energy, filled O2(-) π* orbital and an empty low-lying O2(-) π* orbital in [3](1-).

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Citations

Apr 15, 2016·Inorganic Chemistry·Paraskevi O LagaditisSven Schneider
Jun 9, 2016·Journal of Chemical Theory and Computation·Dongxia MaLaura Gagliardi
Dec 23, 2016·Inorganic Chemistry·Qiao ZhangChristian R Goldsmith
Jan 17, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Juha HurmalainenHeikki M Tuononen
Jul 8, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Anne A FischerAdam T Fiedler
Mar 24, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Lin-Lin ZhangChi-Ming Che
Mar 30, 2018·Chemical Communications : Chem Comm· YiligumaGengfeng Zheng
Aug 18, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Katarina SchwalenstockerFeifei Li
May 24, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Conrad A P GoodwinStephen Sproules
Jul 17, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Wade C HenkeJames D Blakemore
May 22, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Shunichi FukuzumiWonwoo Nam
Nov 6, 2020·Chemical Communications : Chem Comm·Ting-Yi ChenWay-Zen Lee
Dec 15, 2020·Chemical Society Reviews·Shunichi FukuzumiWonwoo Nam
Apr 4, 2021·Chemistry : a European Journal·Philip JunkerRainer Streubel
Aug 11, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Deesha D MalikWonwoo Nam
Dec 10, 2016·Inorganic Chemistry·Bongki ShinJaeheung Cho
May 21, 2020·Journal of the American Chemical Society·Andrew J McNeeceJohn S Anderson
Mar 15, 2019·Journal of the American Chemical Society·Atanu RanaAbhishek Dey
Mar 23, 2019·Inorganic Chemistry·Wilson D BaileyWilliam B Tolman
Aug 24, 2021·Journal of the American Chemical Society·Charles WinslowJonathan Rittle

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