scholarly journals On the concept of frustrated Lewis pairs

2017 ◽  
Vol 375 (2101) ◽  
pp. 20170004 ◽  
Author(s):  
Frédéric-Georges Fontaine ◽  
Douglas W. Stephan
Keyword(s):  
Lewis Acid ◽  
Bond Formation ◽  
Frustrated Lewis Pairs ◽  
Metal Chemistry ◽  
Frustrated Lewis Pair ◽  
Acid And Base ◽  
Definition Of ◽  
Lewis Acid And Base ◽  
Pair Work ◽  
Lewis Pairs

In this concept article, we consider the notion of ‘frustrated Lewis pairs’ (FLPs). While the original use of the term referred to steric inhibition of dative bond formation in a Lewis pair, work in the intervening decade demonstrates the limitation of this simplistic view. Analogies to known transition metal chemistry and the applications in other areas of chemistry are considered. In the light of these findings, we present reflections on the criteria for a definition of the term ‘frustrated Lewis pair’. Segregation of the Lewis acid and base and the kinetic nature of FLP reactivity are discussed. We are led to the conclusion that, while an all-inclusive definition of FLP is challenging, the notion of ‘FLP chemistry’ is more readily recognized. This article is part of the themed issue ‘Frustrated Lewis pair chemistry’.

Roles of the Lewis Acid and Base in the Chemical Reduction of CO2 Catalyzed by Frustrated Lewis Pairs

2013 ◽  
Vol 52 (17) ◽  
pp. 10062-10066 ◽  
Author(s):  
Chern-Hooi Lim ◽  
Aaron M. Holder ◽  
James T. Hynes ◽  
Charles B. Musgrave
Keyword(s):  
Lewis Acid ◽  
Chemical Reduction ◽  
Frustrated Lewis Pairs ◽  
Acid And Base ◽  
Lewis Acid And Base ◽  
Reduction Of Co2 ◽  
Lewis Pairs

Theoretical Evaluation of the Efficiency of Novel Frustrated Lewis Pairs in the cis-Hydrogenation Reaction of Dimethylacetylene

2017 ◽  
Vol 42 (4) ◽  
pp. 372-383 ◽  
Author(s):  
Nazanin Noroozi-Shad ◽  
Mostafa Gholizadeh ◽  
Mohammad Izadyar ◽  
Hossein Eshghi
Keyword(s):  
Lewis Acid ◽  
Hydrogenation Reaction ◽  
Lewis Acidity ◽  
Small Molecule Activation ◽  
Frustrated Lewis Pairs ◽  
Theoretical Evaluation ◽  
Wide Range ◽  
Acid And Base ◽  
Lewis Acid And Base ◽  
Lewis Pairs

Frustrated Lewis pairs (FLPs) are the combination of Lewis acid and base motifs where steric hindrance prevents strong adduct formation. Accordingly, the ability of FLPs in small molecule activation and their capability in hydrogen cleavage led to their use in the hydrogenation of a wide range of unsaturated substrates. Here, we investigated theoretically the ability of three intramolecular phosphorus/boron FLPs as bifunctional catalysts in the metal-free hydrogenation of dimethylacetylene to cis-alkene. The mechanism of this hydrogenation reaction, based on the boron acceptor [including –OR substituents (B(OR)2), where R is an aliphatic or aromatic branch] and phosphorus donor, has been explored. Based on the results obtained, it was confirmed that the H2 splitting reaction and the formation of the phosphonium–borohydride motifs for these FLPs are endothermic. It has been shown that these FLPs have a moderate ability in H–H bond splitting. Also, the capability of the boron atom in FLPs on the hydrogenation reaction was investigated. The reduction steps of the mechanism showed an exothermic nature. This result revealed that the presence of the boron as a Lewis acid, with a very limited Lewis acidity, improves the catalytic hydrogenation reaction significantly. Finally, it was confirmed that the proposed FLPs in the cis-hydrogenation of alkynes will be effective.

scholarly journals Lewis acid / Base-free Strategy for the Synthesis of 2-Arylthio and Selenyl Benzothiazole / Thiazole and Imidazole

2021 ◽  
Vol 27 (1) ◽  
pp. 17-23
Author(s):  
Guniganti Balakishan ◽  
Gullapalli Kumaraswamy ◽  
Vykunthapu Narayanarao ◽  
Pagilla Shankaraiah
Keyword(s):  
Lewis Acid ◽  
Bond Formation ◽  
Acid Base ◽  
Mechanistic Pathway ◽  
Wide Range ◽  
Acid And Base ◽  
Lewis Acid And Base ◽  
Sulfur Bond

Abstract A Cu(II)-catalyzed Csp2-Se and Csp2-Sulfur bond formation was achieved with moderate to good yields without the aid of Lewis acid and base. The reaction is compatible with a wide range of heterocycles such as benzothiazole, thiazole, and imidazole. Also, this typical protocol is found to be active in thio-selenation via S-H activation. Additionally, we proposed a plausible mechanistic pathway involving Cu(III) putative intermediate.

scholarly journals Exploiting the Electronic Tuneability of Carboranes as Supports for Frustrated Lewis Pairs

Molecules ◽  
2018 ◽  
Vol 23 (12) ◽  
pp. 3099 ◽  
Author(s):  
Amanda Benton ◽  
Zachariah Copeland ◽  
Stephen M. Mansell ◽  
Georgina M. Rosair ◽  
Alan J. Welch
Keyword(s):  
Lewis Acid ◽  
Michael Addition ◽  
Coupling Constants ◽  
Frustrated Lewis Pairs ◽  
Acid Component ◽  
Frustrated Lewis Pair ◽  
Lewis Pairs

The first example of a carborane with a catecholborolyl substituent, [1-Bcat-2-Ph-closo-1,2-C2B10H10] (1), has been prepared and characterized and shown to act as the Lewis acid component of an intermolecular frustrated Lewis pair in catalyzing a Michael addition. In combination with B(C6F5)3 the C-carboranylphosphine [1-PPh2-closo-1,2-C2B10H11] (IVa) is found to be comparable with PPh2(C6F5) in its ability to catalyze hydrosilylation, whilst the more strongly basic B-carboranylphosphine [9-PPh2-closo-1,7-C2B10H11] (V) is less effective and the very weakly basic species [μ-2,2ʹ-PPh-{1-(1ʹ-1ʹ,2ʹ-closo-C2B10H10)-1,2-closo-C2B10H10}] (IX) is completely ineffective. Base strengths are rank-ordered via measurement of the 1J 31P-77Se coupling constants of the phosphineselenides [1-SePPh2-closo-1,2-C2B10H11] (2), [9-SePPh2-closo-1,7-C2B10H11] (3), and [SePPh2(C6F5)] (4).

Intramolecular cooperativity in frustrated Lewis pairs

2016 ◽  
Vol 52 (64) ◽  
pp. 9949-9952 ◽  
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.

Bis(perchlorocatecholato)silane and Heteroleptic Bidonors: Hidden Frustrated Lewis Pairs by Ring Strain

2021 ◽  
Author(s):  
Deborah Hartmann ◽  
Sven Braner ◽  
Lutz Greb
Keyword(s):  
Ammonia Borane ◽  
Frustrated Lewis Pairs ◽  
Ring Strain ◽  
Frustrated Lewis Pair ◽  
Lewis Pairs

Bis(perchlorocatecholato)silane and bidentate N,N- or N,P-heteroleptic donors form hexacoordinated complexes. Depending on the ring strain and hemilability in the adducts, Frustrated Lewis pair reactivity with aldehydes and catalytic ammonia borane...

Development of silica-supported frustrated Lewis pairs: highly active transition metal-free catalysts for the Z-selective reduction of alkynes

2016 ◽  
Vol 6 (3) ◽  
pp. 882-889 ◽  
Author(s):  
Kai C. Szeto ◽  
Wissam Sahyoun ◽  
Nicolas Merle ◽  
Jessica Llop Castelbou ◽  
Nicolas Popoff ◽  
...  
Keyword(s):  
Transition Metal ◽  
Lewis Acid ◽  
Selective Reduction ◽  
Frustrated Lewis Pairs ◽  
Acid Base ◽  
Metal Free ◽  
Highly Active ◽  
Active Transition ◽  
Lewis Pairs

Supported Lewis acid/base systems based have been prepared and characterized.

Combined theoretical and experimental study on alcoholysis of amides on CeO2 surface: A catalytic interplay between Lewis acid and base sites

2018 ◽  
Vol 303 ◽  
pp. 256-262 ◽  
Author(s):  
Takashi Kamachi ◽  
S.M.A. Hakim Siddiki ◽  
Yoshitsugu Morita ◽  
Md. Nurnobi Rashed ◽  
Kenichi Kon ◽  
...  
Keyword(s):  
Experimental Study ◽  
Lewis Acid ◽  
Acid And Base ◽  
Lewis Acid And Base
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