Systematic Design of a Frustrated Lewis Pair Containing Methyleneborane and Carbene for Dinitrogen Activation

Rouf, Alvi Muhammad; Huang, Yuanyuan; Dong, Shicheng; Zhu, Jun

doi:10.1021/acs.inorgchem.0c03520

Cited by 39 publications

(27 citation statements)

References 91 publications

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“…A similar relation between aromaticity and activation power of FLPs was observed by Zhuang et al [97] in a DFT study on CO 2 activation. Rouf et al [98] demonstrated an increase in the reaction feasibility of dinitrogen activation by FLPs due to an increase in aromaticity. A DFT-based study performed by Trujillo et al [94] shows the effect of aromaticity in the activation power of FLPs.…”

Section: Activation Of Other Small Moleculesmentioning

confidence: 99%

“…A similar relation between aromaticity and activation power of FLPs was observed by Zhuang et al [97] in a DFT study on CO2 activation. Rouf et al [98] demonstrated an increase in the reaction feasibility of dinitrogen activation by FLPs due to an increase in aromaticity. Some reactions with FLPs were discovered a few years ago, such as Nsulfinyltolylamine (p-TolNSO) yielding a seven-membered cyclic product where binding occurs via N and O centers of p-TolNSO [46].…”

Section: Activation Of Other Small Moleculesmentioning

confidence: 99%

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Activation of Small Molecules and Hydrogenation of CO2 Catalyzed by Frustrated Lewis Pairs

2022

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The chemistry of frustrated Lewis pair (FLP) is widely explored in the activation of small molecules, the hydrogenation of CO2, and unsaturated organic species. A survey of several experimental works on the activation of small molecules by FLPs and the related mechanistic insights into their reactivity from electronic structure theory calculation are provided in the present review, along with the catalytic hydrogenation of CO2. The mechanistic insight into H2 activation is thoroughly discussed, which may provide a guideline to design more efficient FLP for H2 activation. FLPs can activate other small molecules like, CO, NO, CO2, SO2, N2O, alkenes, alkynes, etc. by cooperative action of the Lewis centers of FLPs, as revealed by several computational analyses. The activation barrier of H2 and other small molecules by the FLP can be decreased by utilizing the aromaticity criterion in the FLP as demonstrated by the nucleus independent chemical shift (NICS) analysis. The term boron-ligand cooperation (BLC), which is analogous to the metal-ligand cooperation (MLC), is invoked to describe a distinct class of reactivity of some specific FLPs towards H2 activation.

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Section: Activation Of Other Small Moleculesmentioning

confidence: 99%

“…A similar relation between aromaticity and activation power of FLPs was observed by Zhuang et al [97] in a DFT study on CO2 activation. Rouf et al [98] demonstrated an increase in the reaction feasibility of dinitrogen activation by FLPs due to an increase in aromaticity. Some reactions with FLPs were discovered a few years ago, such as Nsulfinyltolylamine (p-TolNSO) yielding a seven-membered cyclic product where binding occurs via N and O centers of p-TolNSO [46].…”

Section: Activation Of Other Small Moleculesmentioning

confidence: 99%

Activation of Small Molecules and Hydrogenation of CO2 Catalyzed by Frustrated Lewis Pairs

2022

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“…因为此方法不需要使用钌、铑、铱、钯等贵金属, 可以有效避免金属残留和催化剂失活等问题, 目前已引起各国科研工作者极大的研究兴趣 [19] . 截止目前, FLPs 已作为催化剂被应用于亚胺、烯胺、烯烃、多芳香烃、炔烃、酮和醛等不饱和化合物的氢化反应 [12,[20][21][22][23][24][25][26][27][28][29][30] ; 此外, 有报道显示: FLPs 还能活化 N 2 、CO 2 、SO 2 、NO、CO、N 2 O 等小分子 [31][32][33][34][35] , 进一步扩展了 FLPs 化学的范畴.…”

Section: 引言unclassified

Mechanism of Silyl Enol Ethers Hydrogenation Catalysed by Frustrated Lewis Pairs: A Theoretical Study

Wang¹,

Wei²,

Duan³

et al. 2021

Acta Chimica Sinica

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Silyl enol ethers have attracted enormous attention as they could serve as a test bed for the development of novel frustrated Lewis pairs (FLPs) catalytic systems. However, the reaction mechanism of hydrogenation catalysed by metal-free FLPs for these compounds to the corresponding secondary alcohols remains elusive to a large extent in previous studies. We thus performed a thorough investigation on the reaction mechanism by density functional theory (DFT). To illustrate the reaction mechanism of FLPs-catalysed hydrogenation for silyl enol ethers, trimethyl((1-phenylvinyl)oxy)silane (Me-TMS) was chosen as the prototype substrate and toluene as the solvent, where the FLPs were generated by ethylbis(perfluorophenyl)borane (Et-B(C6F5)2) and tri-tert-butylphosphine (t-Bu3P). The M06-2X functional in connection with 6-31＋G(d) basis set was used to optimize the structures of related species including in the Gibbs free energy profiles, and the energies were obtained at M06-2X/6-311＋＋G(d,p) level of theory, where the solvent effect was simulated with the integral equation formalism, polarized continuum mode (IEF-PCM) in both calculations. Our results suggest that the FLPs-catalysed hydrogenation of silyl enol ethers in toluene begins with the formation of B-P-FLPs followed by hydrogen activation, proton transfer and hydride transfer to complete the process. It is obvious from the Gibbs free energy profile that the proton transfer is rate-determining step, the formation of B-P-FLPs and proton transfer are endothermal and the hydride transfer is no barrier. This indicates that the amount of H2 and prototype substrate have significant influence on the FLPs-catalysed hydrogenation of silyl enol ethers. A higher temperature (328.15 K) is disadvantageous to hydrogenation reaction catalysed by FLPs but the reaction could be accelerated under higher pressure (4040 kPa). The Gibbs free energy profile calculations for trimethyl((1-phenylprop-1-en-1-yl)oxy)silane (Et-TMS) and tert-butyldimethyl((1-phenylvinyl)oxy)silane (Me-TBS) reveal that substituent group may inhibit the hydride transfer as the absence of a suitable construction for R-H --transfer, where the hydride does not direct to the C ＋ of silyl enol ethers and the distance between C ＋ and hydride is longer. These results would be helpful to design another novel FLPs-catalysed hydrogenation reaction for silyl enol ethers.

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“…Aromaticity [48][49][50][51] is a fundamental concept in chemistry that usually improves the stability of compounds with a wide range of applications to singlet fission [52][53][54] as well as reaction mechanisms, e.g., N 2 activation, [55][56][57][58] C-F bond activation, 59,60 and CO 2 capture. 61 In contrast, antiaromaticity usually leads to instability.…”

Section: Introductionmentioning

confidence: 99%

Antiaromaticity-promoted radical anion stability in α-vinyl heterocyclics

Lin

Zhu

2022

Org. Chem. Front.

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Systematic Design of a Frustrated Lewis Pair Containing Methyleneborane and Carbene for Dinitrogen Activation

Cited by 39 publications

References 91 publications

Activation of Small Molecules and Hydrogenation of CO2 Catalyzed by Frustrated Lewis Pairs

Activation of Small Molecules and Hydrogenation of CO2 Catalyzed by Frustrated Lewis Pairs

Mechanism of Silyl Enol Ethers Hydrogenation Catalysed by Frustrated Lewis Pairs: A Theoretical Study

Antiaromaticity-promoted radical anion stability in α-vinyl heterocyclics

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