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12.4: Alkyne Acidity - Formation of Acetylide Anions

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    After completing this section, you should be able to

    1. write an equation for the reaction that occurs between a terminal alkyne and a strong base, such as sodamide, NaNH2.
    2. rank a given list of compounds, including water, acetylene and ammonia, in order of increasing or decreasing acidity.
    3. rank a given list of hydrocarbons, such as acetylene, ethylene and ethane, in order of increasing or decreasing acidity.
    4. describe a general method for determining which of two given compounds is the stronger acid.
    5. provide an acceptable explanation of why terminal alkynes are more acidic than alkanes or alkenes.
    Key Terms

    Make certain that you can define, and use in context, the key terms below.

    • acetylide anion
    • acidity order
    Study Notes

    An acetylide anion is an anion formed by removing the proton from the end carbon of a terminal alkyne:

    propyne reacts with sodium metal and a strong base to give an acetylide anion.svg

    An acidity order is a list of compounds arranged in order of increasing or decreasing acidity.

    The general ideas discussed in this section should already be familiar to you from your previous exposure to chemistry and from the review in Section 2.8. A slightly different account of why terminal alkynes are stronger acids than are alkenes or alkanes is given below. However, the argument is still based on the differences between sp-, sp2- and sp3-hybrid orbitals.

    The carbons of a triple bond are sp-hybridized. An sp‑hybrid orbital has a 50% s character and a 50% p character, whereas an sp2‑hybrid orbital is 33% s and 67% p, and an sp3‑hybrid orbital is 25% s and 75% p. The greater the s character of the orbital, the closer the electrons are to the nucleus. Thus in a C(sp)-H bond, the bonding electrons are closer to the carbon nucleus than they are in a C(sp2)-H bond. In other words, compared to a C(sp2)-H bond (or a C(sp3)-H bond), a C(sp)-H bond is very slightly polar: Cδ-Hδ+. This slight polarity makes it easier for a base to remove a proton from a terminal alkyne than from a less polar or non-polar alkene or alkane.

    As you will appreciate, the reaction between sodium amide and a terminal alkyne is an acid-base reaction. The sodium acetylide product is, of course, a salt. Terminal alkynes can also form salts with certain heavy-metal cations, notably silver(I) and copper(I). In the laboratory component of this course, you will use the formation of an insoluble silver acetylide as a method for distinguishing terminal alkynes from alkenes and non-terminal alkynes:

    silver cations react with terminal alkynes in ammonium hydroxide:ethanol to give a silver acetylide, which is a white precipitate. internal alkynes and alkenes do not react under these conditions.svg

    Metal acetylides are explosive when dry. They should be destroyed while still wet by warming with dilute nitric acid:

    a silver acetylide will react with acid to give an alkyne plus silver cation.svg

    Acidity of Terminal Alkynes: Formation of Acetylide Anions

    Terminal alkynes are much more acidic than most other hydrocarbons. Removal of the terminal proton leads to the formation of an acetylide anion, RC≡C:.

    Mechanism for reaction of a terminal alkyne with sodium amide to give an acetylide anion plus ammonia..svg

    As discussed in Section 2.10, acidity typically increases with the stability of the corresponding conjugate base. The origin of the enhanced acidity of terminal alkynes can be attributed to the stability of the acetylide anion, which has the unpaired electrons in an sp hybridized orbital. The hybridization of an orbital affects its electronegativity. Within a shell, the s orbitals occupy the region closer to the nucleus than the p orbitals. Therefore, the spherical s orbitals are more electronegative than the lobed p orbitals. The relative electronegativity of hybridized orbitals increases as the percent s character increases and follows the order sp > sp2 > sp3.

    effect of hybridization on anion stability, where alkyl anions (25%s) are least stable, then vinyl anions (33%s), and acetylide anion (50%s) are the most stable.svg

    This trend indicates the sp hybridized orbitals of the acetylide anion are more electronegative and better able to stabilize a negative charge than sp2 or sp3 hybridized orbitals. There is a strong correlation between s-character in the orbital containing the non-bonding electrons in the anion and the acidity of hydrocarbons. The table below shows how orbital hybridization compares with the identity of the atom when predicting relative acidity. Remember that as the pKa of a compound decreases its acidity increases.

    Table \(\PageIndex{1}\): Akynes
    Compound Conjugate Base Hybridization "s Character" pKa C-H BDE (kJ/mol)
    CH3CH3 CH3CH2 sp3 25% 50 410
    CH2CH2 CH2CH sp2 33% 44 473
    HCCH HCC sp 50% 25 523

    Acetylene, with a pKa of 25 is shown to be much more acidic than ethylene (pKa = 44) or ethane (pKa = 50). Consequently, acetylide anions can be readily formed by deprotonation of a terminal alkynes with a sufficiently strong base. The amide anion (NH2-), in the form of sodium amide (NaNH2)​ is commonly used for the formation of acetylide anions.

    Example \(\PageIndex{1}\)

    1-pentyne reacts with sodium amide to give an acetylide.svg

    ethynylcyclopentane reacts with sodium amide to give an acetylide.svg

    Exercise  \(\PageIndex{1}\)

    Given that the pKa of water is 14.00, would you expect hydroxide ion to be capable of removing a proton from each of the substances listed below? Justify your answers, briefly.

    1. ethanol (pKa = 16)
    2. acetic acid (pKa = 4.72)
    3. acetylene (pKa = 25)

    a. No, not very well. The pKa of ethanol is greater than that of water, thus the equilibrium lies to the left rather than to the right.Add texts here. Do not delete this text first.

    hydroxide reacts with ethanol to give water and ethoxide, which favors the reactants (left hand side).svg

    b. Yes, very well. There is a difference of 11 pKa units between the pKa of water and the pKa of acetic acid. The equilibrium lies well to the right.

    hydroxide reacts with acetic acid to give water and acetate, which favors the products (right hand side).svg

    c. No, hardly at all. The hydroxide ion is too weak a base to remove a proton from acetylene. The equilibrium lies well to the left.

    hydroxide reacts with acetylene to give water and acetylide, which favors the reactants (left hand side).svg

    12.4: Alkyne Acidity - Formation of Acetylide Anions is shared under a CC BY-SA 4.0 license and was authored, remixed, and/or curated by Steven Farmer, Dietmar Kennepohl, Layne Morsch, William Reusch, Paul G. Wenthold, & Paul G. Wenthold.