Electronic structure and reactivity of nickel(i) pincer complexes: their aerobic transformation to peroxo species and site selective C-H oxygenation

Chemical Science
Christoph A RettenmeierLutz H Gade

Abstract

The study is aimed at a deeper understanding of the electronic structure of the T-shaped nickel(i) complex [LigiPr(iso)Ni] (1b), bearing the iso-PyrrMeBox (bis(oxazolinylmethylidene)pyrrolidinido) pincer ligand, and its CO adduct [LigiPr(iso)Ni(CO)] (2b) as well as to provide insight into the mechanism of autoxidation of the different nickel peroxo species of this ligand type. CO was found to react reversibly with complex 1b resulting in the corresponding CO adduct 2b. The EPR data as well as the results of DFT modeling revealed significant differences in the electronic structure of 1b and 2b. Reaction of [LigPh(iso)Ni] and [LigiPr(iso)Ni] (1a and b) with dioxygen yielded the 1,2-μ-peroxo complexes [Lig(iso)NiO]23a and b which reacted with hydrogen peroxide to give the hydroperoxo complexes [Lig(iso)NiOOH] 5a and b. Thermal aerobic decomposition of the peroxo species 3a and 5a in the presence of O2 led to a C-H activation of the ligand at the benzylic position of the oxazoline ring forming diastereomeric cyclic peroxo complexes 6 and 6'. For the 1,2-μ-peroxo complex 3b the autoxidation of the pincer in the absence of O2 occurred at the tertiary C-H bond of the iPr-group and led to a selective formation of the terminal hydroxo c...Continue Reading

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Sep 13, 2001·Journal of the American Chemical Society·B S MandimutsiraC G Riordan
Oct 24, 2001·Inorganic Chemistry·Hidehito KomatsuzakiYoshihiko Moro-Oka
Nov 7, 1996·Chemical Reviews·Stephen W. Ragsdale, Manoj Kumar
May 25, 2004·Inorganic Chemistry·Koyu FujitaCharles G Riordan
Oct 20, 2004·Accounts of Chemical Research·Eric L Hegg
Feb 24, 2006·Journal of the American Chemical Society·Melanie C DenneyKaren I Goldberg
Sep 28, 2006·Chemical Communications : Chem Comm·Takayuki NagatakiShinobu Itoh
Nov 2, 2006·Journal of the American Chemical Society·Matthew T Kieber-EmmonsCharles G Riordan
Mar 7, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Takayuki NagatakiShinobu Itoh
Apr 20, 2007·Proceedings of the National Academy of Sciences of the United States of America·Maurice BrookhartGerard Parkin
May 24, 2007·Accounts of Chemical Research·Matthew T Kieber-Emmons, Charles G Riordan
Dec 25, 2007·Inorganic Chemistry·Michael J InglesonKenneth G Caulton
Jul 1, 2008·Nature Reviews. Microbiology·Rudolf K ThauerReiner Hedderich
Dec 2, 2008·Angewandte Chemie·Shiro HikichiMunetaka Akita
Nov 17, 2009·Biochimica Et Biophysica Acta·Isabel A Abreu, Diane E Cabelli
Mar 20, 2010·Annual Review of Biochemistry·Rudolf K ThauerSeigo Shima
Mar 25, 2010·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Kelly C RyanMichael J Maroney
Jun 8, 2011·Metallomics : Integrated Biometal Science·Güneş BenderStephen W Ragsdale
Aug 31, 2011·Accounts of Chemical Research·Shenglai Yao, Matthias Driess
Jul 31, 2012·Journal of the American Chemical Society·Debabrata MukherjeeAaron D Sadow
Apr 16, 2013·Journal of the American Chemical Society·Jun NakazawaShiro Hikichi
Mar 25, 2014·Chemical Reviews·Wolfgang LubitzEdward Reijerse
Aug 29, 2014·Accounts of Chemical Research·Qing-Hai DengLutz H Gade

❮ Previous
Next ❯

Citations

Apr 13, 2019·Angewandte Chemie·Tomasz PietrzakJanusz Lewiński
Jan 22, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Dasol ChoMu-Hyun Baik
Nov 18, 2016·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Adam T Fiedler, Anne A Fischer
Jul 5, 2017·Chemical Society Reviews·Chun-Yi Lin, Philip P Power
Feb 16, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Hao-Ching ChangWay-Zen Lee
May 21, 2020·Journal of the American Chemical Society·Andrew J McNeeceJohn S Anderson
Jun 18, 2021·Chemistry, an Asian Journal·Arpan DasSwadhin K Mandal
Feb 9, 2017·Journal of the American Chemical Society·Philipp Zimmermann, Christian Limberg
Oct 2, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Kouki Matsubara

❮ Previous
Next ❯

Methods Mentioned

BETA
X-ray
ESR
NMR

Related Concepts

Related Feeds

Alternative Complement Pathway

The Alternative Complement Pathway is part of the innate immune system, and activation generates membrane attack complexes that kill pathogenic cells. Discover the latest research on the Alternative Complement Pathway.