Carbene-Based Lewis Pairs for Hydrogen Activation

A series of Lewis acid–base pairs containing sterically demanding carbenes were investigated for hydrogen activation that could potentially be reversible for use in hydrogen storage applications. When electron-rich boranes are employed as electrophiles, the imidazolium cation is reduced to a 2H-imidazoline (aminal). The aminals were synthesized independently by reduction of imidazolium cations with strong reducing agents. Carbocations were also found to act as electrophiles for hydrogen activation. Preliminary results revealed that it is possible to reduce an alcohol to an alkane using hydrogen gas as a reducing agent in these systems. Finally, it was demonstrated that a transition metal can be used as an electrophile to activate hydrogen through heterolytic cleavage.

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Diverse bimetallic mechanisms emerging from transition metal Lewis acid/base pairs: development of co-catalysis with metal carbenes and metal carbonyl anions

Chemical Communications ◽

10.1039/c7cc09675e ◽

2018 ◽

Vol 54 (11) ◽

pp. 1291-1302 ◽

Cited By ~ 28

Author(s):

Neal P. Mankad

Keyword(s):

Transition Metal ◽

Lewis Acid ◽

Cooperative Behavior ◽

Metal Carbonyl ◽

Catalytic Reactions ◽

Acid Base ◽

Base Pairs ◽

Rational Development ◽

Metal Carbenes

The rational development of catalytic reactions involving cooperative behavior between two catalytic reactive sites represents a frontier area of research from which novel reactivity and selectivity patterns emerge.

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

Catalysis Science & Technology ◽

10.1039/c5cy01372k ◽

2016 ◽

Vol 6 (3) ◽

pp. 882-889 ◽

Cited By ~ 21

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.

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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

Chemical Science ◽

10.1039/c5sc04070a ◽

2016 ◽

Vol 7 (3) ◽

pp. 2331-2334 ◽

Cited By ~ 16

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.

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

ChemInform ◽

10.1002/chin.201316040 ◽

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

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

Catalysis Science & Technology ◽

10.1039/c7cy02541f ◽

2018 ◽

Vol 8 (4) ◽

pp. 1134-1141 ◽

Cited By ~ 13

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.

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A Transition Metal Lewis Acid/Base Triad System for Cooperative Substrate Binding

Journal of the American Chemical Society ◽

10.1021/ja400962h ◽

2013 ◽

Vol 135 (9) ◽

pp. 3403-3406 ◽

Cited By ~ 45

Author(s):

Oscar Tutusaus ◽

Chengbao Ni ◽

Nathaniel K. Szymczak

Keyword(s):

Transition Metal ◽

Lewis Acid ◽

Substrate Binding ◽

Acid Base

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

Journal of the American Chemical Society ◽

10.1021/ja307374j ◽

2012 ◽

Vol 134 (42) ◽

pp. 17384-17387 ◽

Cited By ~ 149

Author(s):

Patrick Eisenberger ◽

Adrian M. Bailey ◽

Cathleen M. Crudden

Keyword(s):

Lewis Acid ◽

Acid Base ◽

Base Pairs

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Thermodynamics of several lewis-acid-base stabilized transition metal alloys

Metallurgical Transactions A ◽

10.1007/bf02646841 ◽

1984 ◽

Vol 15 (11) ◽

pp. 2075-2085 ◽

Cited By ~ 28

Author(s):

John K. Gibson ◽

Leo Brewer ◽

Karl A. Gingerich

Keyword(s):

Transition Metal ◽

Lewis Acid ◽

Metal Alloys ◽

Acid Base ◽

Transition Metal Alloys

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Coordination Chemistry of N,N′-Bis(diphenylphosphanylmethyl)- 2,3-dihydro-1H-perimidine – Lewis Acid-Base Complexes with the d10-Metals Nickel(0) and Gold(I)

Zeitschrift für Naturforschung B ◽

10.5560/znb.2014-4150 ◽

2014 ◽

Vol 69 (11-12) ◽

pp. 1299-1305 ◽

Cited By ~ 4

Author(s):

Sven Krieck ◽

Daniel Schulze ◽

Helmar Görls ◽

Matthias Westerhausen

Keyword(s):

Coordination Chemistry ◽

Transition Metal ◽

Metal Complexes ◽

Transition Metal Complexes ◽

Lewis Acid ◽

Nickel Complexes ◽

Nickel Atom ◽

Addition Reactions ◽

Acid Base ◽

Tetrahedral Environment

Abstract The addition reactions of N,N′-bis(diphenylphosphanylmethyl)-2,3-dihydro-1H-perimidine (1) with [(cod)2Ni] and [(Ph3P)AuCl] yield yellow [(1)Ni(η4-cod)] (2) and colorless [(1)(Ph3P)AuCl]·3MeOH (3), respectively. In these transition metal complexes of nickel(0) and gold(I) 1 acts as a bidentate chelating ligand. Crystal structures of [(1)Ni(η4-cod)]·3THF (2a) and of cosolvent-free [(1)Ni(η4-cod)] (2) reveal a distorted tetrahedral environment of the nickel atom. The gold(I) atom in 3 exhibits a very long Au-Cl bond of 296.2(1) pm. In contrast to the nickel complexes, compound 3 shows strong agostic interactions between gold(I) and a methylene fragment.

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