Gold catalyzed hydrogenations of small imines and nitriles: enhanced reactivity of Au surface toward H2via collaboration with a Lewis base

Gang Lu; Peng Zhang; Dongqing Sun; Lei Wang; Kebin Zhou; Zhi-Xiang Wang; Guo-Cong Guo

doi:10.1039/c3sc52851k

Gold catalyzed hydrogenations of small imines and nitriles: enhanced reactivity of Au surface toward H2via collaboration with a Lewis base

Chemical Science ◽

10.1039/c3sc52851k ◽

2014 ◽

Vol 5 (3) ◽

pp. 1082-1090 ◽

Cited By ~ 49

Author(s):

Gang Lu ◽

Peng Zhang ◽

Dongqing Sun ◽

Lei Wang ◽

Kebin Zhou ◽

...

Keyword(s):

Lewis Acid ◽

Lewis Base ◽

Frustrated Lewis Pair

Au (111) surface can serve as a Lewis acid to couple with a Lewis base (e.g. imine or nitrile) to form the Au-coupled FLP (frustrated Lewis pair, left) which can cleave H2, further achieving hydrogenation of small imines and nitriles.

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Developing carbon Lewis base/boron Lewis acid frustrated Lewis pair chemistry derived from conjugated dienamines

Tetrahedron ◽

10.1016/j.tet.2018.11.068 ◽

2019 ◽

Vol 75 (5) ◽

pp. 571-579 ◽

Cited By ~ 3

Author(s):

Jennifer Möricke ◽

Florian Rehwinkel ◽

Tobias Danelzik ◽

Constantin G. Daniliuc ◽

Birgit Wibbeling ◽

...

Keyword(s):

Lewis Acid ◽

Lewis Base ◽

Frustrated Lewis Pair

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Recent Advances in Water-Tolerance in Frustrated Lewis Pair Chemistry

Synthesis ◽

10.1055/s-0037-1609843 ◽

2018 ◽

Vol 50 (09) ◽

pp. 1783-1795 ◽

Cited By ~ 17

Author(s):

Michael Ingleson ◽

Valerio Fasano

Keyword(s):

Small Molecules ◽

Lewis Acid ◽

Lewis Acids ◽

Short Review ◽

Lewis Base ◽

Small Molecule Activation ◽

Significant Progress ◽

Water Tolerance ◽

Frustrated Lewis Pair ◽

Main Challenge

A water-tolerant frustrated Lewis pair (FLP) combines a sterically encumbered Lewis acid and Lewis base that in synergy are able to activate small molecules even in the presence of water. The main challenge introduced by water comes from its reversible coordination to the Lewis acid which causes a marked increase in the Brønsted acidity of water. Indeed, the oxophilic Lewis acids typically used in FLP chemistry form water adducts whose acidity can be comparable to that of strong Brønsted acids such as HCl, thus they can protonate the Lewis base component of the FLP. Irreversible proton transfer quenches the reactivity of both the Lewis acid and the Lewis base, precluding small molecule activation. This short review discusses the efforts to overcome water-intolerance in FLP systems, a topic that in less than five years has seen significant progress.1 Introduction2 Water-Tolerance (or Alcohol-Tolerance) in Carbonyl Reductions3 Water-Tolerance with Stronger Bases4 Water-Tolerant Non-Boron-Based Lewis Acids in FLP Chemistry5 Conclusions

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Intramolecular cooperativity in frustrated Lewis pairs

Chemical Communications ◽

10.1039/c6cc05228b ◽

2016 ◽

Vol 52 (64) ◽

pp. 9949-9952 ◽

Cited By ~ 14

Author(s):

Leif A. Körte ◽

Sebastian Blomeyer ◽

Shari Heidemeyer ◽

Andreas Mix ◽

Beate Neumann ◽

...

Keyword(s):

Lewis Acid ◽

Lewis Base ◽

Frustrated Lewis Pairs ◽

Frustrated Lewis Pair ◽

Fast Exchange ◽

Lewis Pairs

The doubly Lewis-acid functionalised aniline PhN[(CH2)3B(C6F5)2]2 features two competing boron functions in fast exchange for binding to the central Lewis base. In contrast to the mono acid-functionalised PhMeN[(CH2)3B(C6F5)2], it is an active frustrated Lewis pair.

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Design and reactions of a carbon Lewis base/boron Lewis acid frustrated Lewis pair

Philosophical Transactions of The Royal Society A Mathematical Physical and Engineering Sciences ◽

10.1098/rsta.2017.0015 ◽

2017 ◽

Vol 375 (2101) ◽

pp. 20170015 ◽

Cited By ~ 5

Author(s):

Jennifer Möricke ◽

Birgit Wibbeling ◽

Constantin G. Daniliuc ◽

Gerald Kehr ◽

Gerhard Erker

Keyword(s):

Sulfur Dioxide ◽

Lewis Acid ◽

Lewis Base ◽

Addition Reactions ◽

Acid Interaction ◽

Frustrated Lewis Pair ◽

Hb C

The conjugated dienamine 4 selectively adds Piers' borane [HB(C 6 F 5 ) 2 ] to give the enamine/borane system 5 , which features a boratirane structure by internal enamine carbon Lewis base to boron Lewis acid interaction. Compound 5 behaves as a C/B frustrated Lewis pair and undergoes typical addition reactions to benzaldehyde, several nitriles and to sulfur dioxide. This article is part of the themed issue ‘Frustrated Lewis pair chemistry’.

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Living polymerization of naturally renewable butyrolactone-based vinylidenes mediated by a frustrated Lewis pair

Polymer Chemistry ◽

10.1039/d1py00924a ◽

2021 ◽

Vol 12 (38) ◽

pp. 5548-5555

Author(s):

Yun Bai ◽

Huaiyu Wang ◽

Jianghua He ◽

Yuetao Zhang

Keyword(s):

Lewis Acid ◽

Living Polymerization ◽

Controlled Polymerization ◽

Frustrated Lewis Pair

The frustrated Lewis pair composed of an organophosphorus(iii) superbase and a bulky organoaluminum Lewis acid promoted the living/controlled polymerization of naturally renewable butyrolactone-based vinylidenes.

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Multiple-pathways of carbon dioxide binding by a Lewis acid [B(C6F5)3] and a lewis base [P(tBu)3]: The energy landscape perspective

International Journal of Quantum Chemistry ◽

10.1002/qua.24558 ◽

2013 ◽

Vol 114 (4) ◽

pp. 289-294 ◽

Cited By ~ 6

Author(s):

Maoping Pu ◽

Timofei Privalov

Keyword(s):

Carbon Dioxide ◽

Lewis Acid ◽

Energy Landscape ◽

Lewis Base

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The structure and activity of potassium supported on SBA-15 molecular sieve: Density functional theory study

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633613500764 ◽

2014 ◽

Vol 13 (01) ◽

pp. 1350076 ◽

Cited By ~ 2

Author(s):

Bing Liu ◽

Daxi Wang ◽

Zhongxue Wang ◽

Zhen Zhao ◽

Yu Chen ◽

...

Keyword(s):

Density Functional Theory ◽

Lewis Acid ◽

Molecular Sieve ◽

Active Sites ◽

Density Functional ◽

Structural Model ◽

Vibrational Frequencies ◽

Oxygen Molecule ◽

Lewis Base ◽

Functional Theory

The geometries, vibrational frequencies, electronic properties and reactivity of potassium supported on SBA-15 have been theoretically investigated by the density functional theory (DFT) method. The structural model of the potassium supported on SBA-15 was constructed based on our previous work [Wang ZX, Wang DX, Zhao Z, Chen Y, Lan J, A DFT study of the structural units in SBA-15 mesoporous molecular sieve, Comput. Theor. Chem.963, 403, 2011]. This paper is the extension of our previous work. The most favored location of potassium atom was obtained by the calculation of substitution energy. The calculated vibrational frequencies of K /SBA-15 are in good agreement with the experimental results. By analyzing the properties of electronic structure, we found that the O atom of Si - O (2)- K group acts as the Lewis base center and the K atom acts as the Lewis acid center. The reactivity of K /SBA-15 was investigated by calculating the activation of oxygen molecule. The oxygen molecule can be activated by K /SBA-15 with an energy barrier of 103.2 kJ/mol. In the final state, the activated oxygen atoms become new Lewis acid centers, which are predicted to act as the active sites in the catalytic reactions. This study provides a deep insight into the properties of supported potassium catalysts and offers fundamental information for further research.

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