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用于铑催化的芳烃和烷烃C-H硼化反应的催化剂设计：氮杂环卡宾影响诱导期，且茚基优于环戊二烯基。

Catalyst Design for Rh-Catalyzed Arene and Alkane C-H Borylation: The NHC Affects the Induction Period, and Indenyl is Superior to Cp.

作者信息

Morton Paul A, Boyce Abigayle L, Pišpek Anamarija, Stewart Lennox W, Ward Daniel J, Tegner Bengt E, Macgregor Stuart A, Mansell Stephen M

机构信息

Institute of Chemical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, U.K.

出版信息

Organometallics. 2024 Mar 28;43(9):974-986. doi: 10.1021/acs.organomet.4c00025. eCollection 2024 May 13.

DOI:10.1021/acs.organomet.4c00025
PMID:38756993
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11094794/
Abstract

In order to establish design criteria for Rh C-H borylation catalysts, analogues of the successful catalyst [Rh(Ind)(SIDipp)(COE)] (Ind = η-indenyl, SIDipp = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene, and COE = -cyclooctene) were synthesized by changing the indenyl and carbene ligands. [RhCp(SIDipp)(COE)] () formed alongside the C-C activated, cyclometalated byproduct [RhCp(κC,C-SIDipp')(Pr)] (; SIDipp' = 1-(6-isopropylphenyl)-3-(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene). Computational modeling of COE dissociation showed that both C-C and C-H activation of the SIDipp aryl group is thermally attainable and reversible under experimental conditions, with the C-C activation products being the more thermodynamically stable species. Oxidative addition of with SiH(OEt) gave the Rh silyl hydride [RhCp(H){Si(OEt)}(SIDipp)] (). [Rh(Ind)(IDipp)(COE)] (; IDipp = 1,3-bis(2,6-diisopropylphenyl)-imidazole-2-ylidene), the carbonyl analogue [Rh(Ind)(IDipp)(CO)] (; ν = 1940 cm, cf. 1944 cm for [Rh(Ind)(SIDipp)(COE)]), and [Rh(Ind)(IMe)(COE)] (; IMe = 1,3,4,5-tetramethylimidazol-2-ylidene) were also characterized, but attempts to synthesize Rh carbene complexes with fluorenyl or 1,2,3,4-tetrahydrofluorenyl ligands were not successful. For the catalytic C-H borylation of benzene using Bpin, was inactive at 80 °C, and [Rh(Ind)(SIDipp)(COE)] was superior to all other complexes tested due to the shortest induction period. However, the addition of HBpin to precatalyst eliminated the induction period. Catalytic -alkane C-H borylation using [Rh(Ind)(NHC)(COE)] gave yields of up to 21% alkylBpin, but [RhCp*(CH)] was the better catalyst.

摘要

为了建立用于Rh C-H硼化催化剂的设计标准，通过改变茚基和卡宾配体合成了成功的催化剂[Rh(Ind)(SIDipp)(COE)]（Ind = η-茚基，SIDipp = 1,3-双(2,6-二异丙基苯基)-4,5-二氢咪唑-2-亚基，COE = -环辛烯）的类似物。[RhCp(SIDipp)(COE)]（）与C-C活化的、环金属化的副产物[RhCp(κC,C-SIDipp')(Pr)]（；SIDipp' = 1-(6-异丙基苯基)-3-(2,6-二异丙基苯基)-4,5-二氢咪唑-2-亚基）一起形成。COE解离的计算模型表明，在实验条件下，SIDipp芳基的C-C和C-H活化在热学上是可以实现的且是可逆的，C-C活化产物是热力学上更稳定的物种。与SiH(OEt)进行氧化加成得到铑硅氢化物[RhCp(H){Si(OEt)}(SIDipp)]（）。还对[Rh(Ind)(IDipp)(COE)]（；IDipp = 1,3-双(2,6-二异丙基苯基)-咪唑-2-亚基）、羰基类似物[Rh(Ind)(IDipp)(CO)]（；ν = 1940 cm，相比之下[Rh(Ind)(SIDipp)(COE)]为1944 cm）和[Rh(Ind)(IMe)(COE)]（；IMe = 1,3,4,5-四甲基咪唑-2-亚基）进行了表征，但尝试合成具有芴基或1,2,3,4-四氢芴基配体的铑卡宾配合物未成功。对于使用Bpin对苯进行催化C-H硼化反应，在80℃下无活性，并且由于诱导期最短，[Rh(Ind)(SIDipp)(COE)]优于所有其他测试的配合物。然而，向预催化剂中加入HBpin消除了诱导期。使用[Rh(Ind)(NHC)(COE)]进行催化 -烷烃C-H硼化反应，烷基Bpin的产率高达21%，但[RhCp*(CH)]是更好的催化剂。

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