The divergent effects of strong NHC donation in catalysis.
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ABSTRACT: Strong σ-donation from NHC ligands (NHC = N-heterocyclic carbene) is shown to have profoundly conflicting consequences for the reactivity of transition-metal catalysts. Such donation is regarded as central to high catalyst activity in many contexts, of which the second-generation Grubbs metathesis catalysts (RuCl2(NHC)(PCy3)([double bond, length as m-dash]CHPh), GII) offer an early, prominent example. Less widely recognized is the dramatically inhibiting impact of NHC ligation on initiation of GII, and on re-entry into the catalytic cycle from the resting-state methylidene species RuCl2(NHC)(PCy3)([double bond, length as m-dash]CH2), GIIm. Both GII and the methylidene complexes are activated by dissociation
SUBMITTER: Lummiss JAM
PROVIDER: S-EPMC5947514 | biostudies-literature | 2015 Dec
REPOSITORIES: biostudies-literature
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