Design Platform for Sustainable Catalysis with Radicals: Electrochemical Activation of Cp2TiCl2 for Catalysis Unveiled

被引：13

作者：

Hilche, Tobias ^{[1
]}

Reinsberg, Philip H. ^{[2
]}

Klare, Sven ^{[1
]}

Liedtke, Theresa ^{[1
]}

Schaefer, Luise ^{[1
]}

Gansaeuer, Andreas ^{[1
]}

机构：

[1] Univ Bonn, Kekule Inst Organ Chem & Biochem, Gerhard Domagk Str 1, D-53121 Bonn, Germany

[2] Univ Bonn, Inst Phys & Theoret Chem, Romerstr 164, D-53117 Bonn, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2021年 / 27卷 / 15期

关键词：

catalysis; density functional calculations; electrochemistry; radicals; screening; RING-DISC ELECTRODES; METAL-FREE; TITANOCENE; REDUCTION; MECHANISM; COMPLEXES; ARYLATION; KINETICS;

D O I：

10.1002/chem.202004519

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The combination of synthesis, rotating ring-disk electrode (RRDE) and cyclic voltammetry (CV) measurements, and computational investigations with the aid of DFT methods shows how a thiourea, a squaramide, and a bissulfonamide as additives affect the EqCr equilibrium of Cp2TiCl2. We have, for the first time, provided quantitative data for the EqCr equilibrium and have determined the stoichiometry of adduct formation of [Cp2Ti(III)Cl-2](-), [Cp2Ti(III)Cl] and [Cp2Ti(IV)Cl-2] and the additives. By studying the structures of the complexes formed by DFT methods, we have established the Gibbs energies and enthalpies of complex formation as well as the adduct structures. The results not only demonstrate the correctness of our use of the EqCr equilibrium as predictor for sustainable catalysis. They are also a design platform for the development of novel additives in particular for enantioselective catalysis.

引用

页码：4903 / 4912

页数：10

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