Gutmann–Beckett method

The Gutmann–Beckett method is an experimental procedure used by chemists to assess the Lewis acidity of molecular species. Triethylphosphine oxide (Et3PO, TEPO) is used as a probe molecule and systems are evaluated by 31P NMR spectroscopy.

Acids and bases
Acid types
Base types

Gutmann (1975) used 31P NMR spectroscopy to parameterize Lewis acidity of solvents by Acceptor Numbers.[1] Beckett (1996) recognised its more generally utility and adapted the procedure so that it could be easily applied to molecular species when dissolved in weakly Lewis acidic solvents.[2] However, it has been shown that there is no one universal order of Lewis acid strengths (or Lewis base strengths) and that two parameters or two properties are needed (see HSAB theory and ECW model) to define acid and base strengths.[3] Single parameter or property scales are limited to a smaller range of acids or bases. The term Gutmann–Beckett method was first used in chemical literature in 2007[4] and the Gutmann-Beckett method is in current use (as a single parameter procedure) due to its experimental convenience.

Prof. Dr Viktor Gutmann (1921–98) was an eminent Austrian chemist (see de:Viktor Gutmann) renowned for his work on non-aqueous solvents. Prof. Michael A. Beckett is a former Head of the School of Chemistry at Bangor University, UK.

Application to boranes
Interaction of triethylphosphine oxide with a Lewis acid

The 31P chemical shift (δ) of Et3PO is sensitive to chemical environment but can usually be found between +40 and +100 ppm. The O atom in Et3PO is a Lewis base, and its interaction with Lewis acid sites causes deshielding of the adjacent P atom. Gutmann described an Acceptor Number (AN) scale for solvent Lewis acidity [5] with two reference points relating to the 31P NMR chemical shift of Et3PO in the weakly Lewis acidic solvent hexane (δ = 41.0 ppm, AN 0) and in the strongly Lewis acidic solvent SbCl5 (δ = 86.1 ppm, AN 100). Acceptor numbers can be calculated from AN = 2.21 x (δsample – 41.0) and higher AN values indicate greater Lewis acidity. Boron trihalides are archetypal Lewis acids and have the following AN values: BF3 (89) < BCl3 (106) < BBr3 (109) < BI3 (115).[2] The Lewis acidity of other molecules can be obtained in weakly Lewis acidic solvents by 31P NMR measurements of their Et3PO adducts.[6] The Gutmann–Beckett method has been applied to Lewis acids derived fluoroarylboranes [6][7] such as B(C6F5)3 (AN 82), and borenium cations, and its application to a variety of boron compounds has been reviewed.[8]

Application to other compounds

The Gutmann–Beckett method has been successfully applied to alkaline earth metal complexes,[9][10] p-block main group compounds [6][11][12][13][14] (e.g. AlCl3, AN 87; silylium cations; [E(bipy)2]3+ (E = P, As, Sb, Bi) cations; cationic 4 coordinate Pv and Sbv derivatives) and transition-metal compounds [6][15] (e.g. TiCl4, AN 70).

References
  1. U. Mayer, V. Gutmann, and W. Gerger, "The acceptor number – a quantitative empirical parameter for the electrophilic properties of solvents", Monatshefte fur Chemie, 1975, 106, 1235–1257. doi: 10.1007/BF00913599
  2. M.A. Beckett, G.C. Strickland, J.R. Holland, and K.S. Varma, "A convenient NMR method for the measurement of Lewis acidity at boron centres: correlation of reaction rates of Lewis acid initiated epoxide polymerizations with Lewis acidity", Polymer, 1996, 37, 4629–4631. doi: 10.1016/0032-3861(96)00323-0
  3. R.E. Cramer and T.T. Bopp, (1977) "Great E and C plot. Graphical display of the enthalpies of adduct formation for Lewis acids and bases", Journal of Chemical Education, 1977, 54, 612-613. doi: 10.1021/ed054p612
  4. G.C. Welch, L.Cabrera, P.A. Chase, E. Hollink, J.M. Masuda, P. Wei, and D.W. Stephan,"Tuning Lewis acidity using the reactivity of "frustrated Lewis pairs": facile formation of phosphine-boranes and cationic phosphonium-boranes", Dalton Trans., 2007, 3407–3414. doi: 10.1039/b704417h
  5. V. Gutmann, "Solvent effects on reactivities of organometallic compounds", Coord. Chem. Rev., 1976, 18, 225–255. doi: 10.1016/S0010-8545(00)82045-7
  6. M.A. Beckett, D.S. Brassington, S.J. Coles, and M.B. Hursthouse, "Lewis acidity of tris(pentafluorophenyl)borane: crystal and molecular structure of B(C6F5)3.OPEt3", Inorg. Chem. Commun., 2000, 3, 530–533. doi: 10.1016/S1387-7003(00)00129-5
  7. S.C. Binding, H. Zaher, F.M. Chadwick, and D. O'Hare, "Heterolytic activation of hydrogen using frustrated Lewis pairs containing tris(2,2',2'-perfluorobiphenyl)borane", Dalton Trans., 2012, 41, 9061–9066. doi: 10.1039/c2dt30334e
  8. I.B. Sivaev, V.L. Bregadze, “Lewis acidity of boron compounds”, Coord. Chem. Rev., 2014, 270/271, 75-88. doi: 10.1016/j.ccr.2013.10.017
  9. S. Brand, J. Pahl, H. Elsen, and S. Harder, "Frustrated Lewis pair chemistry with magnesium Lewis acids", European J. Inorg. Chem., 2017, 4187-4195. doi: 10.1002/ejic.201700787
  10. J. Pahl, S. Brand, H. Elsen, and S. Harder,"Highly Lewis acidic cationic alkaline earth metal complexes", Chem. Commun., 2018, 54, 8685-8688. doi: 10.1039/C8CC04083D
  11. H. Grossekappenberg, M. Reissmann, M. Schmidtmann, and T. Mueller, “Quantitative assessment of the Lewis acidity of silylium ions”, Organometallics, 2015, 34, 4952-4958. doi: 10.1021/acs.organomet.5b00556
  12. S.S. Chitnis, A.P.M. Robertson, N. Burford, B.O. Patrick, R. McDonald, and M.J. Ferguson, “Bipyridine complexes of E3+ (E = P, As, Sb, Bi): strong Lewis acids, sources of E(OTf)3 and synthons for EI and Ev cations”, Chemical Sciences, 2015, 6, 6545-6555. doi: 10.1039/C5SC02423D
  13. J.M. Bayne and D.W. Stephan, “Phosphorus Lewis acids: emerging reactivity and applications in catalysis”, Chem. Soc. Rev., 2015, 45, 765-774. doi:10.1039/c5cs00516g
  14. B. Pan and F. Gabbai, “[Sb(C6H5)4][B(C6F5)4]: an air stable Lewis acidic stibonium salt that activates strong element-fluorine bonds”, J. Am. Chem. Soc., 2014, 136, 9564-9567. doi: 10.1021/ja505214m
  15. C.-Y. Wu, T. Horibe, C.B. Jacobsen, and D. Toste, “Stable gold(III) catalysts by oxidative addition of a carbon-carbon bond”, Nature, 2015, 517, 449-454. doi: 10.1038/nature14104
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