For Publishers
DiscoveryMetadataPeer reviewHostingPublishing
For Researchers
JoinPublishReviewCollect
Register
Blog
About
Search
Advanced search
My ScienceOpen
Search
For Publishers
For Researchers
Blog
About
16
views
64
references
 Top references
cited by
10
    
0 reviews
 Review
0
comments
 Comment
0
recommends
+1 Recommend
0 collections
    0
    shares
      0
      similar
       All similar
      • Record: found
      • Abstract: found
      • Article: found
      Is Open Access

      Fluorinated antimony(v) derivatives: strong Lewis acidic properties and application to the complexation of formaldehyde in aqueous solutions†

      research-article
      Author(s): a , a ,
      Publication date (Electronic):
      Journal: Chemical Science
      Publisher: Royal Society of Chemistry

      Read this article at

      ScienceOpenPublisherPMC
      Bookmark
          There is no author summary for this article yet. Authors can add summaries to their articles on ScienceOpen to make them more accessible to a non-specialist audience.

          Abstract

          Lewis acidic fluorinated organoantimony( v) derivatives have been combined with phosphines for the complexation and colourimetric sensing of formaldehyde in biphasic water/CH 2Cl 2 mixtures.

          Abstract

          As part of our ongoing studies of water tolerant Lewis acids, we have synthesized and investigated the properties of Sb(C 6F 5) 3(O 2C 6Cl 4), a fluorinated stiborane whose Lewis acidity approaches that of B(C 6F 5) 3. While chloroform solutions of this Lewis acid can be kept open to air or exposed to water for extended periods of time, this new Lewis acid reacts with P t Bu 3 and paraformaldehyde to form the corresponding formaldehyde adduct t Bu 3P–CH 2–O–Sb(C 6F 5) 3(O 2C 6Cl 4). To test if this reactivity can also be observed with systems that combine the phosphine and the stiborane within the same molecule, we have also prepared o-C 6H 4(PPh 2)(SbAr 2(O 2C 6Cl 4)) (Ar = Ph, C 6F 5). These yellow compounds, which possess an intramolecular P→Sb interaction, are remarkably inert to water but do, nonetheless, react with and accomodate formaldehyde into the P/Sb pocket. In the case of the fluorinated derivative o-C 6H 4(PPh 2)(Sb(C 6F 5) 2(O 2C 6Cl 4)), formaldehyde complexation, which occurs in water/dichloromethane biphasic mixtures, is accompanied by a colourimetric turn-off response thus highlighting the potential that this chemistry holds in the domain of molecular sensing.

          Related collections

          Most cited references64

          • Record: found
          • Abstract: found
          • Article: not found

          Molecular single-bond covalent radii for elements 1-118.

          Pekka Pyykkö, Michiko Atsumi (2009)
          A self-consistent system of additive covalent radii, R(AB)=r(A) + r(B), is set up for the entire periodic table, Groups 1-18, Z=1-118. The primary bond lengths, R, are taken from experimental or theoretical data corresponding to chosen group valencies. All r(E) values are obtained from the same fit. Both E-E, E-H, and E-CH(3) data are incorporated for most elements, E. Many E-E' data inside the same group are included. For the late main groups, the system is close to that of Pauling. For other elements it is close to the methyl-based one of Suresh and Koga [J. Phys. Chem. A 2001, 105, 5940] and its predecessors. For the diatomic alkalis MM' and halides XX', separate fits give a very high accuracy. These primary data are then absorbed with the rest. The most notable exclusion are the transition-metal halides and chalcogenides which are regarded as partial multiple bonds. Other anomalies include H(2) and F(2). The standard deviation for the 410 included data points is 2.8 pm.
          Article 0 comments Cited 332 times – based on 0 reviews     Review now
            Bookmark
            • Record: found
            • Abstract: found
            • Article: not found

            A cartography of the van der Waals territories.

            Santiago Álvarez (2013)
            The distribution of distances from atoms of a particular element E to a probe atom X (oxygen in most cases), both bonded and intermolecular non-bonded contacts, has been analyzed. In general, the distribution is characterized by a maximum at short E···X distances corresponding to chemical bonds, followed by a range of unpopulated distances--the van der Waals gap--and a second maximum at longer distances--the van der Waals peak--superimposed on a random distribution function that roughly follows a d(3) dependence. The analysis of more than five million interatomic "non-bonded" distances has led to the proposal of a consistent set of van der Waals radii for most naturally occurring elements, and its applicability to other element pairs has been tested for a set of more than three million data, all of them compared to over one million bond distances.
            Article 0 comments Cited 190 times – based on 0 reviews     Review now
              Bookmark
              • Record: found
              • Abstract: found
              • Article: not found

              Frustrated Lewis pairs: from concept to catalysis.

              Douglas W Stephan (2015)
              CONSPECTUS: Frustrated Lewis pair (FLP) chemistry has emerged in the past decade as a strategy that enables main-group compounds to activate small molecules. This concept is based on the notion that combinations of Lewis acids and bases that are sterically prevented from forming classical Lewis acid-base adducts have Lewis acidity and basicity available for interaction with a third molecule. This concept has been applied to stoichiometric reactivity and then extended to catalysis. This Account describes three examples of such developments: hydrogenation, hydroamination, and CO2 reduction. The most dramatic finding from FLP chemistry was the discovery that FLPs can activate H2, thus countering the long-existing dogma that metals are required for such activation. This finding of stoichiometric reactivity was subsequently evolved to employ simple main-group species as catalysts in hydrogenations. While the initial studies focused on imines, subsequent studies uncovered FLP catalysts for a variety of organic substrates, including enamines, silyl enol ethers, olefins, and alkynes. Moreover, FLP reductions of aromatic anilines and N-heterocycles have been developed, while very recent extensions have uncovered the utility of FLP catalysts for ketone reductions. FLPs have also been shown to undergo stoichiometric reactivity with terminal alkynes. Typically, either deprotonation or FLP addition reaction products are observed, depending largely on the basicity of the Lewis base. While a variety of acid/base combinations have been exploited to afford a variety of zwitterionic products, this reactivity can also be extended to catalysis. When secondary aryl amines are employed, hydroamination of alkynes can be performed catalytically, providing a facile, metal-free route to enamines. In a similar fashion, initial studies of FLPs with CO2 demonstrated their ability to capture this greenhouse gas. Again, modification of the constituents of the FLP led to the discovery of reaction systems that demonstrated stoichiometric reduction of CO2 to either methanol or CO. Further modification led to the development of catalytic systems for the reduction of CO2 by hydrosilylation and hydroboration or deoxygenation. As each of these areas of FLP chemistry has advanced from the observation of unusual stoichiometric reactions to catalytic processes, it is clear that the concept of FLPs provides a new strategy for the design and application of main-group chemistry and the development of new metal-free catalytic processes.
              Article 0 comments Cited 180 times – based on 0 reviews     Review now
                Bookmark
                All references

                Author and article information

                Journal
                Journal ID (nlm-ta): Chem Sci
                Journal ID (iso-abbrev): Chem Sci
                Title: Chemical Science
                Publisher: Royal Society of Chemistry
                ISSN (Print): 2041-6520
                ISSN (Electronic): 2041-6539
                Publication date (Print): 01 November 2016
                Publication date (Electronic): 11 July 2016
                Volume: 7
                Issue: 11
                Pages: 6768-6778
                Affiliations
                [a ] Department of Chemistry , Texas A&M University , College Station , TX 77843 , USA . Email: francois@ 123456tamu.edu
                Article
                Publisher ID: c6sc02558g
                DOI: 10.1039/c6sc02558g
                PMC ID: 5363782
                PubMed ID: 28451122
                SO-VID: 6bb0bf9b-f801-47a2-8d45-e69982fb2e43
                Copyright © This journal is © The Royal Society of Chemistry 2016
                License:

                This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License ( http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

                History
                Date received : 9 June 2016
                Date accepted : 9 July 2016
                Categories
                Subject: Chemistry

                Notes

                †Electronic supplementary information (ESI) available: Additional experimental and computational details and crystallographic data in cif format. CCDC 1483464–1483472. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc02558g


                Data availability:

                Comments

                Comment on this article