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Understanding Electrostatic Potentials in Chemical Reactions

Dive into the world of electrostatic potentials in chemistry with this comprehensive study. Discover the impact of ligand and metal effects on acidity and basicity, and explore how different molecules interact to form adducts with unique properties. This research provides valuable insights for designing new compounds and understanding their behavior in chemical reactions.

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Understanding Electrostatic Potentials in Chemical Reactions

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  1. Dougherty, D. A., Science, 1996, 271,163.

  2. Red = most negative electrostatic potentials (most basic regions) Blue = most positive electrostatic potentials (most acidic regions) Dougherty et al., Proc. Natl. Acad. Sci. USA, Vol. 93, pp. 10566–10571, October 1996 Chemistry

  3. OR p base p acid Burini; Fackler; Omary; Staples et al. J. Am. Chem. Soc. 2000, 122, 11264-11265. TRHg

  4. DFT Calculations of Trinuclear Complexes [Hg(C6F4)]3 [Au(bzim)]3 Electrost. Pot. (a.u.) -0.0300 0.0300

  5. Electrostatic Potential Surfaces [Hg(C6F4)]3 green = positive [Au(bzim)]3 red = negative p-Electrostatic interaction

  6. ADF Calculations {[Au(carb)]3}2 DIMER Green= positive Red=negative

  7. SUPER WHOPPER!! p base p acid p base

  8. SUPRAMOLECULAR CHAIN ASSEMBLIES p base p acid p base p acid Burini; Fackler; Omary; Staples et al. J. Am. Chem. Soc. 2000, 122, 11264-11265.

  9. Solid-state example: p acid p base p acid p base p acid Phosphorescence at RT in the solid-state!! • = 568 ± 8 ms (RT)

  10. Complexation of [Hg(o-C6F4)]3, 1, with aromatic hydrocarbons…RGB bright phosphorescent emissions for the 1:1 solid adducts Omary; Kassab; Haneline; Elbjeirami; Gabbai Inorg. Chem.2003, 42, 2176-2178.

  11. t = 3.6 ms Au3(carb)3.octafluoronaphthalene p acid p base p acid p base

  12. R= e-withdrawing (e.g., CF3) • makes it more of a p acid R= e-releasing (e.g., Me; i-Pr; t-Bu)  makes it more of a p base M= Cu; Ag; Au Metal effect??…

  13. DFT-calculated electrostatic potentials mapped on the electron density surfaces of M3Pz3 complexes. Color code: red=most negative= strong p base; blue=most positive= strong p acid; Yellow= neutral/weak p base green=neutral/weak p acid Cu3Pz3Ag3Pz3,Au3Pz3 Pz ligands here have R=Me groups on them all

  14. All strongp acids But given previous slide we think that the Ag3 compound would be the strongest p acid Calculations done by Alex Gonser, as a CHEM5610 classroom project last year.

  15. SUMMARY • Ligand effect: • R= e-withdrawing (e.g., CF3) • makes it more of a p acid • R= e-releasing (e.g., Me; i-Pr; t-Bu) •  makes it more of a p base Metal effect: Relative p basicity: Au>Cu>Ag Relative p acidity: Ag>Cu>Au M= Cu; Ag; Au If you want to react with naphthalene (p base), what would you choose for R and M to form an acid-base adduct?

  16. Maha Eldabaja (4610 student here doing research in the Omary group)….just got crystals of an adduct for [Ag(3,5-(CF3)2Pz)]3 with naphthalene and found that it has green emission, consistent with naphthalene phosphorescence

  17. Maha Eldabaja (4610 student here doing research in the Omary group)….just got crystals of an adduct for [Ag(3,5-(CF3)2Pz)]3 with naphthalene and found that it has green emission, consistent with naphthalene phosphorescence (let’s hear it for Maha!!) Chi2 : 1.032 Durbin Watson : 1.85 Z : 374.2 Pre-exp. 1 : 825.2 ±1.638E+001 Lifetime 1 : 1.575E+004 ms±6.652E+002 Offset : 26.5 t = ~ 16 ms

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