Establishing the Role of Triflate Anions in H2 Activation by a Cationic Triorganotin(IV) Lewis Acid.
Establishing the Role of Triflate Anions in H2 Activation by a Cationic Triorganotin(IV) Lewis Acid.
复制标题
确定三氟甲磺酸根阴离子在阳离子三有机锡 (IV) 路易斯酸活化 H2 中的作用。
DOI：
10.1021/acscatal.0c02023
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发表时间：
2020
期刊：
影响因子：
12.9
通讯作者：
Sapsford JS
中科院分区：
文献类型：
--
作者：
Sapsford JS
阳离子刘易斯酸（LA）作为受抑的刘易斯对（FLP）介导的催化的靶标越来越受到关注。与中性硼烷不同，中性硼烷是FLP氢化中最常见的LA，阳离子的刘易斯酸性可以通过调节抗衡阴离子来调节;然而，目前文献中缺乏对这种阴离子效应的详细研究。在此，我们提出了实验和计算研究，探索H2活化机制，使用IniPr 3SnOTf（1-OTf）结合配位（奎宁环; qui）和非配位（2，4，6-三甲基吡啶; col）碱，并与{iPr_3Sn·碱}{Al[OC（CF_3）_3]_4}的反应性进行比较。（碱= qui/col）系统，其缺乏配位阴离子以研究负责H2活化的活性物质，并因此解析OTf-在iPr 3SnOTf-介导的途径中的任何机械作用。
Cationic Lewis acids (LAs) are gaining interest as targets for frustrated Lewis pair (FLP)-mediated catalysis. Unlike neutral boranes, which are the most prevalent LAs for FLP hydrogenations, the Lewis acidity of cations can be tuned through modulation of the counteranion; however, detailed studies on such anion effects are currently lacking in the literature. Herein, we present experimental and computational studies which probe the mechanism of H2activation usingiPr3SnOTf (1-OTf) in conjunction with a coordinating (quinuclidine; qui) and noncoordinating (2,4,6-collidine; col) base and compare its reactivity with {iPr3Sn·base}{Al[OC(CF3)3]4} (base = qui/col) systems which lack a coordinating anion to investigate the active species responsible for H2activation and hence resolve any mechanistic roles for OTf–in theiPr3SnOTf-mediated pathway.