Frustrated Lewis pair chemistry of carbon, nitrogen and sulfur oxides

Stephan, Douglas W.; Erker, Gerhard

doi:10.1039/c4sc00395k

Cited by 424 publications

(309 citation statements)

References 98 publications

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“…[15] In the intervening time, several more Reviews about selected aspects of FLP chemistry have appeared. [16] In addition, a two volume set of Topics in Current Chemistry [17] and several specific journal issues [18] as well as several international symposia have been devoted to this topic. In this Review we outline some of the principal lines of development that FLP chemistry has taken in recent years and attempt to provide a perspective for future developments for this young but exciting area of chemistry.…”

Section: Frustrated Lewis Pairs (Flps) Are Combinations Of Lewis Acidmentioning

confidence: 99%

Frustrated Lewis Pair Chemistry: Development and Perspectives

2015

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Frustrated Lewis pairs (FLPs) are combinations of Lewis acids and Lewis bases in solution that are deterred from strong adduct formation by steric and/or electronic factors. This opens pathways to novel cooperative reactions with added substrates. Small-molecule binding and activation by FLPs has led to the discovery of a variety of new reactions through unprecedented pathways. Hydrogen activation and subsequent manipulation in metal-free catalytic hydrogenations is a frequently observed feature of many FLPs. The current state of this young but rapidly expanding field is outlined in this Review and the future directions for its broadening sphere of impact are considered.

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Section: Frustrated Lewis Pairs (Flps) Are Combinations Of Lewis Acidmentioning

confidence: 99%

Frustrated Lewis Pair Chemistry: Development and Perspectives

2015

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“…[1] In the past years, activation of small molecules has become an important research field in inorganic chemistry, although reports on the reactivity of SO2 are scarce. The most succesful approach so far has been the use of frustrated Lewis pairs [2][3] to overcome the weak nucleophilicity of SO2, which even allows its use as a solvent in superacid chemistry. For instance, Gillespie stated that SO2 is not protonated to a significant extent in magic acid (HSO3F/SbF5).…”

Section: +mentioning

confidence: 99%

Isolation and Characterization of a Non‐Rigid Hexamethylbenzene–SO²⁺ Complex

Malischewski

Seppelt

2017

Angew Chem Int Ed

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During our studies towards the preparation of the pentagonal‐pyramidal hexamethylbenzene dication C6(CH3)62+, we isolated the unprecedented dicationic species C6(CH3)6SO2+ (AsF6−)2 from the reaction of hexamethylbenzene with a mixture of anhydrous HF, AsF5, and liquid SO2. This compound can be understood as a complex of unknown SO2+ with hexamethylbenzene. Herein, we report on its synthesis, molecular structure, and spectroscopic characterization.

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“…Although some previous observations already suggested that cooperativity between Lewis pairs could promote metal-free transformations, notably for hydrosilylation [7], it is the use of FLPs for molecular hydrogen activation that led to a surge in research in this field [8][9]. Since, FLPs have been shown to activate many small molecules in addition to being active catalysts in reductive transformations [10][11][12]. The activation of substrates like H2 by transition metal complexes occurs generally by the transfer of electrons from the bond to be cleaved to the LUMO of the metal complex while electrons from the HOMO, either associated with the d orbitals or a ligand in the coordination sphere, are transferred to the anti-bonding orbital (Scheme 1A).…”

Section: Introductionmentioning

confidence: 99%

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

Fontaine

Courtemanche

Légaré

et al. 2017

Coordination Chemistry Reviews

102

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This is the peer reviewed version of the following article: [Design Principles in Frustrated Lewis KeywordsFrustrated Lewis pairs, Ambiphilic molecules, Boron, Aluminum, Carbon dioxide, Methanol, C-H activation. Highlights 1.Phosphine-aluminum frustrated Lewis pairs (FLPs) can activate CO2 but show significant stability issues. 2.The Lewis acidity and basicity need to be fine-tuned to the desired reactivity for efficient FLP catalysis.3. FLP catalysts need to generate strong hydrides to reduce catalytically carbon dioxide. 4.Transition metal catalysis can serve as an inspiration for the design of metal-free catalysts for many transformations, including the borylation of heteroarenes. Graphical abstract AbstractThis account describes our work on the use of ambiphilic molecules as catalysts for the reduction of carbon dioxide. Starting with the discovery that aluminum ambiphilic species (Me2PCH2AlMe2)2 (1) and Al(C6H4-PPh3)3 (5) could coordinate CO2 but showed significant instability, we found that phosphinoborane Ph2P-2-Bcat-C6H4 (7) was an exceptional catalyst for the hydroboration of CO2 to methoxyboranes, a molecule that can be readily hydrolyzed to methanol. A mechanistic investigation allowed us to outline the similarities between the catalytic activity of frustrated Lewis pairs (FLPs) and that of transition metal complexes. We were able to extrapolate four important guidelines, described in this account, to synthesize efficient metal-free catalysts. We demonstrate that using these concepts it was possible to rationally design FLP catalysts for the C-H borylation of heteroarenes.

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Frustrated Lewis pair chemistry of carbon, nitrogen and sulfur oxides

Cited by 424 publications

References 98 publications

Frustrated Lewis Pair Chemistry: Development and Perspectives

Frustrated Lewis Pair Chemistry: Development and Perspectives

Isolation and Characterization of a Non‐Rigid Hexamethylbenzene–SO²⁺ Complex

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

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Frustrated Lewis pair chemistry of carbon, nitrogen and sulfur oxides

Cited by 424 publications

References 98 publications

Frustrated Lewis Pair Chemistry: Development and Perspectives

Frustrated Lewis Pair Chemistry: Development and Perspectives

Isolation and Characterization of a Non‐Rigid Hexamethylbenzene–SO2+ Complex

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

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Isolation and Characterization of a Non‐Rigid Hexamethylbenzene–SO²⁺ Complex