Talk detail - Understanding Nickel’s Role in C(sp3)-H Activation: Structure, Reactivity, & Mechanism

Understanding Nickel’s Role in C(sp3)-H Activation: Structure, Reactivity, & Mechanism

Main list: St Andrews

Abstract

We report a mechanistic study of C(sp3) -H bond activation mediated by nickel. A cyclometalated Ni(II) ureate [(PEt3)Ni(κ3 -C,N,N -(CH2)N(Cy)(CO)N((N) -quinolin -8-yl))] was synthesized and isolated from a urea precursor, (Me)(Cy)N(CO)N(H)(quinolin -8-yl), via C(sp3) -H activation. We investigated the effects of solvents and base additives on the rate of C -H activation. Kinetic isotope effect experiments showed that C -H activation is rate determining. Through deuterium label ling and protonation studies, we also showed that C -H activation can be re versible. We extended this reac tion to a range of ureas with primary and secondary C(sp3) -H bonds, which activate readily to for m analogous nickelated products . Finally, we showed that carboxylate additives assist with both ligand dissociation and initial N-H bond activation, consistent with a concerted metalation deprotonation mechanism.

  • Speaker

    Jennifer Love
    UBC

  • Venue

    Purdie

  • Venue Info

    Theatre C

  • Date

    November 21, 2018

  • Time

    From: 14h00 To: 15h00

  • Sponsor

    ScotCHEM
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