Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
Org Lett. 2010 Jul 2;12(13):2998-3001. doi: 10.1021/ol101014q.
Rate constants for hydrogen abstraction by a nonyl radical from 20 complexes of N-heterocyclic carbenes and boranes (NHC-boranes) have been determined by the pyridine-2-thioneoxycarbonyl (PTOC) competition kinetic method at a single concentration point. The rate constants range from <1 x 10(4) to 8 x 10(4) M(-1) s(-1). They show little dependence on the electronic properties of the carbene core, but there is a trend for increasing rate constants with decreasing size of the carbene N-substituents. Two promising new reagents with small N-substituents (R = Me) have been identified.
已通过吡啶-2-硫代羰酰氧基(PTOC)竞争动力学方法在单一浓度点测定了非自由基从 20 个氮杂环卡宾和硼烷(NHC-硼烷)复合物中夺取氢的速率常数。这些速率常数的范围从<1 x 10(4)到 8 x 10(4) M(-1) s(-1)。它们对卡宾核的电子性质几乎没有依赖性,但随着卡宾 N-取代基体积的减小,速率常数呈上升趋势。已确定了两种具有小 N-取代基(R = Me)的有前途的新型试剂。