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Lewis Acid-Base Interaction in Ph3P-BH3

Overview

Source: Tamara M. Powers, Department of Chemistry, Texas A&M University 

One of the goals of chemistry is to use models that account for trends and provide insights into the properties of reactants that contribute to reactivity. Substances have been classified as acids and bases since the time of the ancient Greeks, but the definition of acids and bases has been modified and expanded over the years.1

The ancient Greeks would characterize substances by taste, and defined acids as those that were sour-tasting, such as lemon juice and vinegar. The term "acid" is derived from the Latin term for "sour-tasting." Bases were characterized by their ability to counteract or neutralize acids. The first bases characterized were those of ashes from a fire, which were mixed with fats to make soap. In fact, the term "alkaline" is derived from the Arabic word for "roasting." Indeed, it has been known since ancient times that acids and bases can be combined to give a salt and water.

The first widely-used description of an acid is that of the Swedish chemist, Svante Arrhenius, who in 1894 defined acids as substances which dissociate in water to give hydronium ions, and bases as substances which dissociate in water to give hydroxide ions. This definition is thus limited to aqueous acids and necessitates that an acid contribute a proton.2 For example, in water, HCl is an acid, as it dissociates to give the hydronium ion (H3O)+ and the chloride ion. Boron trichloride would not be considered an acid, as in water it hydrolyzes to give B(OH)3 and 3 HCl; the product HCl though is an Arrhenius acid.

In 1923, Johannes Nicolaus Brønsted and Martin Lowry independently defined acids and bases on their ability to donate and accept hydrogen ions, or protons. Thus came the concept of acid-base conjugate pairs, and the expansion of the definition of acids and bases in solvents other than water. For example, ammonium is an acid, as it can donate a proton and generate ammonia. Ammonia can accept a proton, to give ammonium. Thus, ammonia is the conjugate base of ammonium. This acid-base reaction can occur in water, ammonia, or other solvents.

This video deals with the acid-base definition of the American chemist, Gilbert N. Lewis, who also defined acids and bases in 1923. Indeed, this is the same Lewis from Lewis-dot structures in General Chemistry. His approach focuses not on the ability of acids and bases to donate and accept protons, but rather on their ability to accept and donate electron pairs, respectively. This encompasses the Brønsted-Lowry definition, as H+ accepts an electron pair from a Brønsted base during protonation. However, it greatly expands the definition of an acid, now encompassing metal ions and main-group compounds. Here, we compare the 31P NMR of the Lewis acid-base adduct Ph3P-BH3 to free triphenylphosphine.

Procedure

1. Setup of the Schlenk Line for the Synthesis of the Borane Triphenylphosphine Complex

NOTE: For a more detailed procedure, please review the "Schlenk Lines Transfer of Solvent" video in the Essentials of Organic Chemistry series). Schlenk line safety should be reviewed prior to conducting this experiment. Glassware should be inspected for star cracks before using. Care should be taken to ensure that O2 is not condensed in the Schlenk line trap if using liquid N

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Results

Borane triphenylphosphine complex:

31P NMR (chloroform-d, 500 MHz, δ, ppm): 20.7 (broad doublet)

Triphenylphosphine:

31P NMR (chloroform-d, 500 MHz, δ, ppm): -5.43

The 31P NMR signal of the borane triphenylphosphine complex is downfield relative to free triphenylphosphine. This is consistent with removal of electron density from the phosphorous center, which is deshielded upon adduct formation.

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Application and Summary

The borane triphenylphosphine complex is an example of a Lewis-adduct, whereby a Lewis base donates electrons to a Lewis acid. Though BH3 and PPh3 would not necessarily be considered an acid and base, respectively, using other acid-base theories, Lewis acid-base theory predicts correctly that the molecules form a stable adduct.

Small Molecule Activation:

While transition metal ions have historically been regarded as Lewis acids

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References
  1. Lesney, Today's Chemist at Work, 2003, 47-48.
  2. Miessler, P. J. Fischer and D. A. Tarr, Inorganic Chemistry, Pearson, 2014.
  3. McNulty, J.; Zhou, Y. Tetrahedron Letters, 2004, 45, 407-409.
  4. Harman and J. C. Peters, J. Am. Chem. Soc., 2012, 134, 5080-5082.
  5. Anderson, J. Rittle and J. C. Peters, Nature, 2013, 501, 84-87.
  6. Stephan, J. Am. Chem. Soc., 2015, 137, 10018-10032.
  7. Welch, R. R. S. Juan, J. D. Masuda and D. W. Stephan, Science, 2006, 314, 1124-1126.
Tags
Lewis Acid basePh3P BH3ChemistryAcid base ModelsReactantsSynthesisSvante ArrheniusDissociateHydronium IonsHydroxide IonsJohannes Br nstedThomas LowryHydrogen IonsSolventsAcid base Conjugate PairsGilbert LewisElectron PairsMetal IonsMain group CompoundsTriphenylphosphine Borane ComplexSynthesis And AnalysisMolecular StructureVSEPR Theory

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0:00

Overview

1:18

Lewis Acid-Base Interactions in Ph3P-BH3

3:15

Schlenk Line Set Up

3:54

Synthesis of Borane Triphenylphosphine Complex

5:39

Work Up, Isolation, and 31P-NMR

6:21

Results

7:08

Applications

8:37

Summary

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