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The Reactivity of Frustrated Lewis Pairs
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The Reactivity of Frustrated Lewis Pairs

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (30 April 2015) | Viewed by 23134

Special Issue Editor

Dr. James D. Hoefelmeyer

E-Mail Website
Guest Editor
Department of Chemistry, University of South Dakota, 414 E. Clark St., Vermillion, SD, USA
Interests: frustrated Lewis pairs; main group chemistry; nanocrystal synthesis; catalysis; solar energy utilization

Special Issue Information

Dear Colleagues,

The observation of heterolytic dissociation of dihydrogen in the presence of a frustrated Lewis pair (FLP) has sparked tremendous interest in FLP chemistry. Most of the effort in this field has been dedicated to synthesis of new FLPs, developing a theoretical understanding of dihydrogen activation, and utilizing FLPs as non-metal hydrogenation catalysts for an increasing variety of unsaturated organic molecules. With these inspiring discoveries, the field is taking exciting new turns with interest toward utilization of FLPs to activate other small molecules (notably CO2) or stabilize unusual molecular fragments, to develop highly preorganized unimolecular FLPs (through synthesis or computation), incorporate FLPs into materials, and devise new schemes in which FLPs catalyze an ever-greater range of reactions. It is also worth mention that the small molecule activation work in this field (i.e. H2, CO2, amine-borane) may have significant implications for energy. The intention of this Special Issue is to create a collection of the latest work with emphasis on synthesis, theoretical work, small molecule activation, catalysis, and comparison between FLPs and transition metal chemistry.

Dr. James D. Hoefelmeyer
Guest Editor

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.


Keywords

  • frustrated lewis pair
  • catalysis
  • coordination
  • computational
  • preorganized
  • materials

Published Papers (3 papers)

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Research

798 KiB  
Article
Chloro({2-[mesityl(quinolin-8-yl-κN)boryl]-3,5-dimethyl-phenyl}methyl-κC)palladium(II) as a Catalyst for Heck Reactions
by Sem Raj Tamang and James D. Hoefelmeyer
Molecules 2015, 20(7), 12979-12991; https://doi.org/10.3390/molecules200712979 - 17 Jul 2015
Cited by 9 | Viewed by 6881
Abstract
We recently reported an air and moisture stable 16-electron borapalladacycle formed upon combination of 8-quinolyldimesitylborane with bis(benzonitrile)dichloropalladium(II). The complex features a tucked mesityl group formed upon metalation of an ortho-methyl group on a mesityl; however it is unusually stable due to contribution [...] Read more.
We recently reported an air and moisture stable 16-electron borapalladacycle formed upon combination of 8-quinolyldimesitylborane with bis(benzonitrile)dichloropalladium(II). The complex features a tucked mesityl group formed upon metalation of an ortho-methyl group on a mesityl; however it is unusually stable due to contribution of the boron pz orbital in delocalizing the carbanion that gives rise to an η4-boratabutadiene fragment coordinated to Pd(II), as evidenced from crystallographic data. This complex was observed to be a highly active catalyst for the Heck reaction. Data of the catalyst activity are presented alongside data found in the literature, and initial comparison reveals that the borapalladacycle is quite active. The observed catalysis suggests the borapalladacycle readily undergoes reductive elimination; however the Pd(0) complex has not yet been isolated. Nevertheless, the ambiphilic ligand 8-quinolyldimesitylborane may be able to support palladium in different redox states. Full article
(This article belongs to the Special Issue The Reactivity of Frustrated Lewis Pairs)
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1069 KiB  
Article
Ambiphilic Frustrated Lewis Pair Exhibiting High Robustness and Reversible Water Activation: Towards the Metal-Free Hydrogenation of Carbon Dioxide
by Étienne Rochette, Marc-André Courtemanche, Alexander P. Pulis, Wenhua Bi and Frédéric-Georges Fontaine
Molecules 2015, 20(7), 11902-11914; https://doi.org/10.3390/molecules200711902 - 29 Jun 2015
Cited by 20 | Viewed by 7726
Abstract
The synthesis and structural characterization of a phenylene-bridged Frustrated Lewis Pair (FLP) having a 2,2,6,6‑tetramethylpiperidine (TMP) as the Lewis base and a 9-borabicyclo[3.3.1]nonane (BBN) as the Lewis acid is reported. This FLP exhibits unique robustness towards the products of carbon dioxide hydrogenation. The [...] Read more.
The synthesis and structural characterization of a phenylene-bridged Frustrated Lewis Pair (FLP) having a 2,2,6,6‑tetramethylpiperidine (TMP) as the Lewis base and a 9-borabicyclo[3.3.1]nonane (BBN) as the Lewis acid is reported. This FLP exhibits unique robustness towards the products of carbon dioxide hydrogenation. The compound shows reversible splitting of water, formic acid and methanol while no reaction is observed in the presence of excess formaldehyde. The molecule is incredibly robust, showing little sign of degradation after heating at 80 °C in benzene with 10 equiv. of formic acid for 24 h. The robustness of the system could be exploited in the design of metal-free catalysts for the hydrogenation of carbon dioxide. Full article
(This article belongs to the Special Issue The Reactivity of Frustrated Lewis Pairs)
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1234 KiB  
Article
Reactivity of Amine/E(C6F5)3 (E = B, Al) Lewis Pairs toward Linear and Cyclic Acrylic Monomers: Hydrogenation vs. Polymerization
by Jiawei Chen and Eugene X.-Y. Chen
Molecules 2015, 20(6), 9575-9590; https://doi.org/10.3390/molecules20069575 - 26 May 2015
Cited by 37 | Viewed by 8163
Abstract
This work reveals the contrasting reactivity of amine/E(C6F5)3 (E = B, Al) Lewis pairs toward linear and cyclic acrylic monomers, methyl methacrylate (MMA) and biorenewable γ-methyl-α-methylene-γ-butyrolactone (γMMBL). While mixing of 2,2,6,6-tetramethylpiperidine (TMP) and B(C6F [...] Read more.
This work reveals the contrasting reactivity of amine/E(C6F5)3 (E = B, Al) Lewis pairs toward linear and cyclic acrylic monomers, methyl methacrylate (MMA) and biorenewable γ-methyl-α-methylene-γ-butyrolactone (γMMBL). While mixing of 2,2,6,6-tetramethylpiperidine (TMP) and B(C6F5)3 leads to a frustrated Lewis pair (FLP), Et3N reacts with B(C6F5)3 to form disproportionation products, ammonium hydridoborate ionic pair and iminium zwitterion. On the other hand, the stoichiometric reaction of either TMP or Et3N with Al(C6F5)3 leads to clean formation of a classic Lewis adduct (CLA). Neither TMP nor Et3N, when paired with E(C6F5)3, polymerizes MMA, but the Et3N/2B(C6F5)3 pair promotes transfer hydrogenation of MMA to form methyl isobutyrate. In contrast, the amine/E(C6F5)3 pairs promote rapid polymerization of γMMBL carrying the more reactive exocyclic methylene moiety, achieving full conversion in less than 3 min even at a low catalyst loading of 0.0625 mol %. TMP is more effective than Et3N for the polymerization when paired with either the borane or the alane, while the alane exhibits higher polymerization activity than the borane when paired with Et3N. Overall, the TMP/Al(C6F5)3 system exhibits the highest polymerization activity, achieving a maximum turn-over frequency of 96,000 h−1 at 0.125 mol % of catalyst loading, producing high molecular weight PγMMBL with Mn = 1.29 × 105 g∙mol−1. Full article
(This article belongs to the Special Issue The Reactivity of Frustrated Lewis Pairs)
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