Skip to main content
SpringerLink
Log in

Probing the Lewis acidity of heavier pnictogen trichlorides

  • Regular Article
  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

Lewis acidity of SbCl3 and BiCl3 has been investigated in the solid as well as in solution state. Two β-ketoimine ligands, [O=C(Me)]CH[C(Me)NHAr] (L1, Ar=2,6-diisopropylphenyl) and [(CH2)2{N(H)C(Me)CHC(Me)=O}2] (L2) are used to prepare the complexes [(L1)(THF)SbCl3]2 (1), [(L1)(THF)BiCl3]2 (2), [L2SbCl3]2 (3) and [(L2)3(BiCl3)2] (4), which are characterized by multinuclear NMR spectroscopy, elemental analysis and single-crystal X-ray diffraction experiments. Solid-state structural analysis of 1–4 and solution studies on SbCl3 and BiCl3 using the Gutmann-Beckett method reveal the higher Lewis acidity of BiCl3 compared to SbCl3.

Graphic abstract

BiCl3 is more Lewis acidic than SbCl3 as evidenced by Gutmann-Beckett analysis and investigation into the solid-state structures of β-ketoimine complexes by single-crystal X-ray diffraction experiments.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4

Similar content being viewed by others

References

  1. (a) Ollevier T 2013 New trends in bismuth-catalyzed synthetic transformations Org. Biomol. Chem. 11 2740; (b) Bothwell J M, Scott W, Krabbe S W and Mohan R S 2011 Applications of bismuth(III) compounds in organic synthesis Chem. Soc. Rev. 40 4649

  2. Norman N C 1994 Coordination chemistry of antimony and bismuth: Lewis acidity, σ ∗ -orbitals and coordination geometry Phosph. Sulfur Silicon Relat. Elem. 87 167

    Article  CAS  Google Scholar 

  3. Kannan R, Kumar S, Andrews A P, Jemmis E D and Venugopal A 2017 Consequence of Ligand bite angle on bismuth Lewis acidity Inorg. Chem. 56 9391

    CAS  Google Scholar 

  4. Balasubramaniam S, Kumar S, Andrews A P, Varghese B, Jemmis E D and Venugopal A 2019 A dicationic bismuth(III) Lewis acid: catalytic hydrosilylation of olefins Eur. J. Inorg. Chem. 3265

    Google Scholar 

  5. Balasubramaniam S, Varghese B and Venugopal A 2019 Bismuth(III) dication trapped on a chlorobismuthate J. Coord. Chem. 72 1417

    Article  CAS  Google Scholar 

  6. (a) Chitnis S S, Vos K A, Burford N, McDonald R and Ferguson M J 2016 Distinction between coordination and phosphine ligand oxidation: interactions of di- and triphosphines with Pn3+ (Pn = P, As, Sb, Bi) Chem. Commun. 52 685; (b) Chitnis S S, Robertson A P M, Burford N, Patrick B O, McDonald R and Ferguson M J 2015 Bipyridine complexes of E3+ (E = P, As, Sb, Bi): strong Lewis acids, sources of E(OTf)3 and synthons for EI and EV cations Chem. Sci. 6 6545; (c) Robertson A P M, Burford N, Gray P A and Ferguson R 2014 Interpnictogen cations: exploring new vistas in coordination chemistry Angew. Chem. Int. Ed. 53 6050; (d) Chitnis S S, Burford N, Decken A and Ferguson M J 2013 Coordination complexes of bismuth triflates with tetrahydrofuran and diphosphine ligands Inorg. Chem. 52 7242

  7. (a) Beckett M A, Strickland G C, Holland J R and Varma K S 1996 A convenient n.m.r. method for the measurement of Lewis acidity at boron centres: correlation of reaction rates of Lewis acid initiated epoxide polymerizations with Lewis acidity Polymer 37 4629; (b) Mayer U, Gutmann V and Gerger W 1975 The acceptor number—A quantitative empirical parameter for the electrophilic properties of solvents Monatsh. Chem. 106 1235

  8. Everett Jr G W and Holm R H 1965 The synthesis and proton resonance study of the solution equilibria of bis(β-ketoamino) nickel(II) complexes J. Am. Chem. Soc. 87 2117

    Article  CAS  Google Scholar 

  9. Gogoi S, Bhuyan R and Barua N C 2005 Iodine-catalyzed conversion of β-dicarbonyl compounds into β-enaminones within a minute under solvent-free conditions Synth. Commun. 35 2811

    CAS  Google Scholar 

  10. (a) Altomare A, Cascarano G, Giacovazzo C and Guagliardi A 1994 J. Appl. Crystallogr. 27 435; (b) Sheldrick G M 2008 A short history of SHELX Acta Cryst. A64 112

  11. Johnson J A, Ashokan A, Chalana A K, Andrews A P and Venugopal A 2017 Neutral and cationic β-ketoiminato bismuth complexes Z. Anorg. Allg. Chem. 643 607

    Article  CAS  Google Scholar 

  12. Cordero B, Gomez V, Platero-prats A E, Rev M, Echeverr J, Cremades E, Barrag F and Alverez S 2008 Covalent radii revisited Dalton Trans. 2832

  13. Adamczyk-wozniak A, Jakubczyk M, Sporzyński A and Żukowska G 2011 Quantitative determination of the Lewis acidity of phenylboronic catechol esters—Promising anion receptors for polymer electrolytes Inorg. Chem. Commun. 14 1753

    CAS  Google Scholar 

  14. Sivaev I B and Bregadze V I 2014 C–H Bond activation of arenes by [8,8′-μ-I-3,3′-Co(1,2-C2B9H10)2] in the presence of sterically hindered Lewis bases Coord. Chem. Rev. 270–271 75

    Google Scholar 

  15. (a) Tsao F A, Waked A E, Cao L, Hofmann J, Liu L, Grimme S and Stephan D W 2016 S(VI) Lewis acids: fluorosulfoxonium cations Chem. Commun. 52 12418; (b) Großekappenberg H, Reißmann M, Schmidtmann M and Müller T 2015 Quantitative assessment of the Lewis acidity of silylium ions Organometallics 34 4952; (c) Pan B and Gabbaï F P 2014 [Sb(C6F5)4][B(C6F5)4]: An air stable, Lewis acidic stibonium salt that activates strong element-fluorine bonds J. Am. Chem. Soc. 136 9564; (d) Caputo C B, Hounjet L J, Dobrovetsky R and Stephan D W 2013 Lewis acidity of organofluorophosphonium salts: hydrodefluorination by a saturated acceptor Science 341 1374

Download references

Acknowledgements

We thank the Council of Scientific and Industrial Research (Grant Number: 01(2777)/14/EMR-II) for the generous funding. Alex P. Andrews is thanked for X-ray diffraction experiments.

Author information

Authors and Affiliations

  1. School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Vithura, Thiruvananthapuram, 695 551, Kerala, India

    Jobha A Johnson & Ajay Venugopal

Authors
  1. Jobha A Johnson
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ajay Venugopal
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ajay Venugopal.

Additional information

Special Issue on 150 years of the Periodic Table

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Johnson, J.A., Venugopal, A. Probing the Lewis acidity of heavier pnictogen trichlorides. J Chem Sci 131, 114 (2019). https://doi.org/10.1007/s12039-019-1706-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s12039-019-1706-6

Keywords

Search

Navigation