Unifying Evaluation of the Technical Performances of Iron-Tetra-amido Macrocyclic Ligand Oxidation Catalysts

Journal of the American Chemical Society
Matthew A DeNardoTerrence J Collins

Abstract

The main features of iron-tetra-amido macrocyclic ligand complex (a sub-branch of TAML) catalysis of peroxide oxidations are rationalized by a two-step mechanism: Fe(III) + H2O2 → Active catalyst (Ac) (kI), and Ac + Substrate (S) → Fe(III) + Product (kII). TAML activators also undergo inactivation under catalytic conditions: Ac → Inactive catalyst (ki). The recently developed relationship, ln(S0/S∞) = (kII/ki)[Fe(III)]tot, where S0 and S∞ are [S] at time t = 0 and ∞, respectively, gives access to ki under any conditions. Analysis of the rate constants kI, kII, and ki at the environmentally significant pH of 7 for a broad series of TAML activators has revealed a 6 orders of magnitude reactivity differential in both kII and ki and 3 orders differential in kI. Linear free energy relationships linking kII with ki and kI reveal that the reactivity toward substrates is related to the instability of the active TAML intermediates and suggest that the reactivity in all three processes derives from a common electronic origin. The reactivities of TAML activators and the horseradish peroxidase enzyme are critically compared.

References

May 1, 1975·Canadian Journal of Biochemistry·D DolmanM D Thurlow
Apr 16, 2002·Science·Sayam Sen GuptaTerrence J Collins
May 5, 2006·Angewandte Chemie·Deboshri BanerjeeTerrence J Collins
Oct 10, 2006·Chemistry : a European Journal·Arani ChandaTerrence J Collins
Dec 23, 2006·Science·Filipe Tiago de OliveiraTerrence J Collins
Aug 30, 2008·Journal of the American Chemical Society·Delia-Laura PopescuTerrence J Collins
Oct 22, 2008·Journal of the American Chemical Society·Anindya GhoshTerrence J Collins
Nov 26, 2009·Journal of the American Chemical Society·W Chadwick EllisTerrence J Collins
Jun 23, 2010·Journal of the American Chemical Society·W Chadwick EllisTerrence J Collins
Aug 10, 2011·Environmental Science & Technology·Longzhu Q ShenTerrence J Collins
Jan 7, 2014·Journal of the American Chemical Society·Munmun GhoshSayam Sen Gupta
Jun 13, 2015·Scientific Reports·Matthew R MillsTerrence J Collins

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Citations

Jan 4, 2017·Journal of the American Chemical Society·Liang L TangTerrence J Collins
Aug 11, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Siva Prasad DasHan Sen Soo
Apr 16, 2020·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Yogesh SomasundarTerrence J Collins
May 12, 2020·Chemical Communications : Chem Comm·Yu-Xin YeGangfeng Ouyang
Jan 20, 2017·Nature Communications·Stefania TomynIgor O Fritsky
Dec 29, 2020·IScience·Yogesh SomasundarTerrence J Collins
Apr 6, 2021·ACS Catalysis·Silvia D'AgostiniDennis G H Hetterscheid
Oct 11, 2016·Journal of the American Chemical Society·Matthew R MillsTerrence J Collins
Aug 14, 2020·Journal of the American Chemical Society·Shan-Shan XueWonwoo Nam
Jan 23, 2019·Inorganic Chemistry·Andrew C WeitzMichael P Hendrich
Jan 9, 2018·Journal of the American Chemical Society·Hao-Yi DuMing-Tian Zhang
May 11, 2017·Chemical Reviews·Terrence J Collins, Alexander D Ryabov

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