A Cobalt(I) Pincer Complex with an η(2) -Caryl -H Agostic Bond: Facile C-H Bond Cleavage through Deprotonation, Radical Abstraction, and Oxidative Addition

Angewandte Chemie
Sathiyamoorthy MurugesanKarl Kirchner

Abstract

The synthesis and reactivity of a Co(I) pincer complex [Co(ϰ(3) P,CH,P-P(CH)P(NMe) -iPr)(CO)2 ](+) featuring an η(2) - Caryl -H agostic bond is described. This complex was obtained by protonation of the Co(I) complex [Co(PCP(NMe) -iPr)(CO)2 ]. The Co(III) hydride complex [Co(PCP(NMe) -iPr)(CNtBu)2 (H)](+) was obtained upon protonation of [Co(PCP(NMe) -iPr)(CNtBu)2 ]. Three ways to cleave the agostic C-H bond are presented. First, owing to the acidity of the agostic proton, treatment with pyridine results in facile deprotonation (C-H bond cleavage) and reformation of [Co(PCP(NMe) -iPr)(CO)2 ]. Second, C-H bond cleavage is achieved upon exposure of [Co(ϰ(3) P,CH,P-P(CH)P(NMe) -iPr)(CO)2 ](+) to oxygen or TEMPO to yield the paramagnetic Co(II) PCP complex [Co(PCP(NMe) -iPr)(CO)2 ](+) . Finally, replacement of one CO ligand in [Co(ϰ(3) P,CH,P-P(CH)P(NMe) -iPr)(CO)2 ](+) by CNtBu promotes the rapid oxidative addition of the agostic η(2) -Caryl -H bond to give two isomeric hydride complexes of the type [Co(PCP(NMe) -iPr)(CNtBu)(CO)(H)](+) .

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Apr 13, 2015·Organometallics·Sathiyamoorthy MurugesanKarl Kirchner

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Citations

May 25, 2016·Journal of the American Chemical Society·Saravanakumar ElangovanMatthias Beller
Aug 2, 2016·Inorganic Chemistry·Linda S JongbloedJarl Ivar van der Vlugt
Aug 5, 2016·Journal of the American Chemical Society·Nicklas Deibl, Rhett Kempe
Mar 14, 2017·Chemical Communications : Chem Comm·M Arif SajjadAlastair J Nielson
Mar 8, 2018·Angewandte Chemie·Qing LuGiovanni Bistoni
Nov 11, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·M Arif SajjadAlastair J Nielson
Sep 6, 2018·Chemistry : a European Journal·Kathrin JungeMatthias Beller
Jan 17, 2020·Angewandte Chemie·Timothy M BoydAndrew S Weller
Jan 13, 2017·Angewandte Chemie·Nicklas Deibl, Rhett Kempe
Sep 28, 2018·Journal of the American Chemical Society·Máté J Bezdek, Paul J Chirik
Sep 17, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Wolfgang EderKarl Kirchner

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