Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E-CH2 -E′ Frustrated Lewis Pairs

2018 ◽  
Vol 24 (67) ◽  
pp. 17823-17831 ◽  
Author(s):  
Jorge Juan Cabrera-Trujillo ◽  
Israel Fernández
Keyword(s):  
Lewis Acid ◽  
Frustrated Lewis Pairs ◽  
Acid Base ◽  
Base Pairs ◽  
Lewis Pairs

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.

scholarly journals Metal–ligand multiple bonds as frustrated Lewis pairs for C–H functionalization

2012 ◽  
Vol 8 ◽  
pp. 1554-1563 ◽  
Author(s):  
Matthew T Whited
Keyword(s):  
Small Molecules ◽  
Metal Species ◽  
Frustrated Lewis Pairs ◽  
Acid Base ◽  
Base Pairs ◽  
Multiple Bonds ◽  
Inorganic Complexes ◽  
Cooperative Activation ◽  
Metal Ligand ◽  
Lewis Pairs

The concept of frustrated Lewis pairs (FLPs) has received considerable attention of late, and numerous reports have demonstrated the power of non- or weakly interacting Lewis acid–base pairs for the cooperative activation of small molecules. Although most studies have focused on the use of organic or main-group FLPs that utilize steric encumbrance to prevent adduct formation, a related strategy can be envisioned for both organic and inorganic complexes, in which "electronic frustration" engenders reactivity consistent with both nucleophilic (basic) and electrophilic (acidic) character. Here we propose that such a description is consistent with the behavior of many coordinatively unsaturated transition-metal species featuring metal–ligand multiple bonds, and we further demonstrate that the resultant reactivity may be a powerful tool for the functionalization of C–H and E–H bonds.

scholarly journals Sc3N@Ih-C80 as a novel Lewis acid to trap abnormal N-heterocyclic carbenes: the unprecedented formation of a singly bonded [6,6,6]-adduct

2016 ◽  
Vol 7 (3) ◽  
pp. 2331-2334 ◽  
Author(s):  
Muqing Chen ◽  
Lipiao Bao ◽  
Min Ai ◽  
Wangqiang Shen ◽  
Xing Lu
Keyword(s):  
Lewis Acid ◽  
Heterocyclic Carbenes ◽  
Acid Base ◽  
Base Pairs ◽  
Endohedral Metallofullerenes ◽  
Carbon Based

An unprecedented singly bonded [6,6,6]-adduct with an abnormal N-heterocyclic carbene structure, represents the first example of carbon-based Lewis acid–base pairs based on endohedral metallofullerenes.

ChemInform Abstract: Taking the F Out of FLP: Simple Lewis Acid-Base Pairs for Mild Reductions with Neutral Boranes via Borenium Ion Catalysis.

ChemInform ◽  
2013 ◽  
Vol 44 (16) ◽  
pp. no-no
Author(s):  
Patrick Eisenberger ◽  
Adrian M. Bailey ◽  
Cathleen M. Crudden
Keyword(s):  
Lewis Acid ◽  
Acid Base ◽  
Base Pairs

scholarly journals Zirconia catalysed acetic acid ketonisation for pre-treatment of biomass fast pyrolysis vapours

2018 ◽  
Vol 8 (4) ◽  
pp. 1134-1141 ◽  
Author(s):  
Hessam Jahangiri ◽  
Amin Osatiashtiani ◽  
James A. Bennett ◽  
Mark A. Isaacs ◽  
Sai Gu ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Lewis Acid ◽  
Fast Pyrolysis ◽  
Acid Sites ◽  
Active Species ◽  
Acid Base ◽  
Lewis Acid Sites ◽  
Base Pairs ◽  
Pre Treatment ◽  
Biomass Fast Pyrolysis

Weak Lewis acid sites (and/or resulting acid–base pairs) on monoclinic ZrO2 are identified as the active species responsible for acetic acid ketonisation to acetone.

Taking the F out of FLP: Simple Lewis Acid–Base Pairs for Mild Reductions with Neutral Boranes via Borenium Ion Catalysis

2012 ◽  
Vol 134 (42) ◽  
pp. 17384-17387 ◽  
Author(s):  
Patrick Eisenberger ◽  
Adrian M. Bailey ◽  
Cathleen M. Crudden
Keyword(s):  
Lewis Acid ◽  
Acid Base ◽  
Base Pairs

A Heterogeneous Metal‐Free Catalyst for Hydrogenation: Lewis Acid–Base Pairs Integrated into a Carbon Lattice

2018 ◽  
Vol 57 (42) ◽  
pp. 13800-13804 ◽  
Author(s):  
Yuxiao Ding ◽  
Xing Huang ◽  
Xianfeng Yi ◽  
Yunxiang Qiao ◽  
Xiaoyan Sun ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Acid Base ◽  
Base Pairs ◽  
Metal Free

scholarly journals Trioxatriangulenium (TOTA+) as a Robust Carbon-based Lewis Acid in Frustrated Lewis Pair Chemistry

2020 ◽  
Author(s):  
Aslam Shaikh ◽  
Jose M Veleta ◽  
Jules Moutet ◽  
thomas Gianetti
Keyword(s):  
Lewis Acid ◽  
Disulfide Bonds ◽  
Variable Temperature ◽  
X Ray Diffraction ◽  
Frustrated Lewis Pairs ◽  
Acid Base ◽  
Base Interaction ◽  
Paramagnetic Resonance ◽  
Heterolytic Cleavage ◽  
Encounter Complex

We report the reactivity between the Lewis acidic trioxotriangulenium ion (TOTA<sup>+</sup>) and a series of Lewis bases such as phosphines and <i>N</i>-heterocyclic carbene (NHC). The nature of the Lewis acid-base interaction was analyzed via variable temperature (VT) NMR spectroscopy, single-crystal X-ray diffraction, UV-visible spectroscopy, and DFT calculations. While small and strongly nucleophilic phosphines, such as PMe<sub>3</sub>, led to the formation of a stable Lewis acid-base adduct, frustrated Lewis pairs (FLPs) were observed for sterically hindered bases such as P(<i><sup>t</sup></i>Bu)<sub>3</sub>. The TOTA<sup>+</sup>-P(<i><sup>t</sup></i>Bu)<sub>3</sub> FLP was characterized as an encounter complex, and was found to promote the heterolytic cleavage of disulfide bonds, formaldehyde fixation, dehydrogenation of 1,4-cyclohexadiene, heterolytic cleavage of C–Br bond, and interception of Staudinger reaction intermediate. Moreover, TOTA<sup>+</sup> and NHC was found to first undergo single-electron transfer (SET) to form [TOTA]<sup>•</sup>[NHC]<sup> •+</sup>, which was confirmed via electron paramagnetic resonance (EPR) spectroscopy, and subsequently form a [TOTA-NHC]<sup>+</sup> adduct or a mixture of products depending the reaction condition used.

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