The mechanism of the (bispidine)copper(II)-catalyzed aziridination of styrene: a combined experimental and theoretical study

Chemistry : a European Journal
Peter CombaMarta Zajaczkowski

Abstract

Experimental and DFT-based computational results on the aziridination mechanism and the catalytic activity of (bispidine)copper(I) and -copper(II) complexes are reported and discussed (bispidine=tetra- or pentadentate 3,7-diazabicyclo[3.1.1]nonane derivative with two or three aromatic N donors in addition to the two tertiary amines). There is a correlation between the redox potential of the copper(II/I) couple and the activity of the catalyst. The most active catalyst studied, which has the most positive redox potential among all (bispidine)copper(II) complexes, performs 180 turnovers in 30 min. A detailed hybrid density functional theory (DFT) study provides insight into the structure, spin state, and stability of reactive intermediates and transition states, the oxidation state of the copper center, and the denticity of the nitrene source. Among the possible pathways for the formation of the aziridine product, the stepwise formation of the two N-C bonds is shown to be preferred, which also follows from experimental results. Although the triplet state of the catalytically active copper nitrene is lowest in energy, the two possible spin states of the radical intermediate are practically degenerate, and there is a spin crossover...Continue Reading

References

Oct 24, 2001·Inorganic Chemistry·Peter BrandtPer-Ola Norrby
Oct 3, 2002·Chemical Society Reviews·J B Sweeney
Apr 16, 2003·Chemistry : a European Journal·Peter CombaYun Xiong
Sep 12, 2006·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Karin BornHubert Wadepohl
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Citations

Jan 19, 2017·Journal of the American Chemical Society·Lourdes MaestrePedro J Pérez
Jul 16, 2014·Chemical Communications : Chem Comm·Sarah-Luise AbramKallol Ray
Nov 26, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Peter CombaHubert Wadepohl
Jun 5, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Peter CombaMiriam Starke
May 8, 2018·Angewandte Chemie·Julian MoeglingSonja Herres-Pawlis
Sep 12, 2009·Chemistry : a European Journal·Peter CombaHubert Wadepohl
Nov 19, 2008·Angewandte Chemie·Yosra M BadieiTimothy H Warren
Nov 20, 2009·Physical Chemistry Chemical Physics : PCCP·Christopher J Cramer, Donald G Truhlar
Jul 24, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Madhavan Jaccob, Gopalan Rajaraman
Dec 18, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Karin BornHeidi Rohwer
Aug 15, 2012·Chemistry : a European Journal·Thi My Uyen TonPhilip Wai Hong Chan
May 9, 2012·Angewandte Chemie·Nicole Jung, Stefan Bräse
May 15, 2013·Chemistry : a European Journal·Jacek Lukasz KolanowskiJens Hasserodt
Oct 19, 2017·Scientific Reports·Zhang BoZhang Jianguo
Apr 29, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Fabian ThomasSonja Herres-Pawlis
Apr 3, 2012·Journal of the American Chemical Society·Thi My Uyen TonPhilip Wai Hong Chan
Nov 28, 2012·The Journal of Organic Chemistry·Qiang WangZhiyong Wang
Nov 8, 2016·ACS Omega·Aleksei V Medved'koSergey Z Vatsadze

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