Chapter 6 Acid Base Chemistry

The Acid Base Theory of Bronsted and Lowry

HCl + H2O == H3O+ + Cl-

Molecular Structure and Acid Strength

H X The stronger the bond H+ + XThe weaker the acid

HF << HCl < HBr < HI

Molecular Structure and Acid Strength

Z dO d+ H Z

O- + H+

The O-H bond will be more polar and easier to break if:
Z is very electronegative or Z is in a high oxidation state

Molecular Structure and Acid Strength

1. Oxoacids having different central atoms (Z) that are from the same group and that have the same oxidation number. Acid strength increases with increasing electronegativity of Z O O H O Cl O H O Br O Cl is more electronegative than Br

HClO3 > HBrO3

Molecular Structure and Acid Strength

2. Oxoacids having the same central atom (Z) but different numbers of attached groups. Acid strength increases as the oxidation number of Z increases.

HClO4 > HClO3 > HClO2 > HClO

Lewis Concept

H+

: NH3

NH4+

2E 3 A1 Energy 2 T2 HOMO

2 A1
1E 1A1

2 A1

1 T2

LUMO

1 A1

1 A1

H+

: NH3

NH4+

2E 3 A1 Energy 2 T2 HOMO

2 A1
1E 1A1

2 A1

1 T2

LUMO

1 A1

1 A1

How do you analyze a mechanism?

Follow the Electrons. Push your arrows.

H
N H H H

N H H H

What orbitals are involved? What are the important MOs of HF and NH3?

* Looks most like H

Lowest Unoccupied Molecular Orbital

H F

H 1s MO diagram of HF Looks most like F

acid LUMO most important

F 2p Highest Ooccupied Molecular Orbital

HF NH3

base HOMO most important

acid LUMO most important

Same Symmetry End On Good Interaction

NH3 HOMO

S (symmetric) No nodes.
HF LUMO

Symmetric-Symmetric S-S Reaction is Symmetry Allowed

Wrong Symmetry No Good Interaction Does not work side on

Restating the Lewis Acid-Base Definition:

a)Base: has e- pair in HOMO of correct energy and symmetry

b)Acid: has LUMO of correct energy and symmetry

Carbon Monoxide as a Lewis Base 1) Electronegativity suggests O is the e- pair donor

C O C O M
+

2) In fact, C is always the donor a) Formal Charge

-1 +1

C O
b)
i.

MO Frontier Orbitals

HOMO that is involved in bonding is mostly on C ii. C-like HOMO donated to the M Lewis acid

O C

The platinum metals are often used in catalysis They have filled d orbitals and empty s or p orbitals. This means they can act as either an acid or a base.

Lewis acid

Lewis acid

Lewis Base

Classes of Lewis bases (Ligands)

Monodentate Ligands - A ligand that donates only one electron pair to a single metal One of the best examples is NH3. Bridging Ligands - A ligand that donates one or more electron pairs to two or more metals Halides and hydroxide are good examples, since each possesses two or more electron pairs on the donor atom As we considered before, one of the steps to forming insoluble hydroxide and oxo compounds is the bridging of two metals in the course of hydroysis.

Classes of Lewis bases cont

Ambidentate Ligands - Ligands that possess two or more donor atoms can act as a monodentate ligand through either donor atom, or bridge two metals. The pseudohalides such as cyanide, azide and thiocyanate are good examples.

Denticity

The number of potential donor interactions is called the denticity ligands are classified as bidentate chelating ligands (as for ethylenediamine), hexadentate chelating ligands (as for ethylenediaminetetraacetic acid; EDTA) and so forth.

Chelating ligands

ethylenediamine (on the left) yields a five-membered ring acetylacetonate (on the right) yields a six-membered ring

N Ni N Ni

Structures of Common Chelating Ligands

2,2-bipyridine (bpy)

N N N

1,10-phenathroline (phen)

terpyridine (terpy)

H2N

NH2

H2N

NH2

H2N

N H

NH2

ethylenediamine (en)

propylenediamine (prn)

diethylenetriamine (dien)

H2N

N H

H N

NH2

N NH2 H2N
tri(ethylenediamine)amine (tren)

NH2

triethylenetetramine (trien)

Macrocyclic ligands

Macrocyclic Ligands - A special class of generally tetradentate chelating ligands, where the four donor atoms are arranged in a circular ring array, as in the porphyrins

14

Increasing Topological Constraint

Coordination

Chelation H2N NH2

Macrocycle Effect

Cryptate Effect

H N H H2N NH3 N NH2 N H N N

N N N N

N N

H H2N N N H NH2

N NH2

[Ni(H2O)6]2+ + n L == [Ni(L)n(H2O)2]2+ + 4 H2O

L= n= NH3 4 en 2 trien 1 2,3,21

H2N

2,3,2

log bn =

8.12

13.5

13.8

14.6

Natures Macrocycle
A porphyrin is any of a group of compounds containing the porphin structure of four pyrrole rings connected by methine bridges in a cyclic configuration, to which a variety of side chains are attached; usually metalled, e.g., with iron to form heme. Definition from Academic Press Dictionary of Science Technology

NH

HN

Porphyrin

The iron(II) protoporphyrin-IX complex is the prosthetic group in hemoglobins and myoglobins, which are responsible for oxygen transport and storage in living tissues. Heme can also be found in the enzyme peroxidase, which catalyzes the oxidation of substrates with hydrogen peroxide. Other hemecontaining proteins include the cytochromes, which serve as one-electron carriers in the electron transport chain.

Reduction of one of the pyrrole units on the porphyrin ring leads to a class of porphyrin derivatives called chlorins. Chlorophylls (e.g. chlorophyll-a), found abundantly in green plants, belong to this category. They play very important roles in the process of photosynthesis.

Porphyrins are also found in other systems such as the wing feathers of Turacus indicus , the oxygen-carrying pigment chlorocruorin from Sabella starte indica , oil shale, and some marine sponges.

Vitamin B12 contains a porphyrin-like unit called corrin

Type of non- protic acid- base reactions

Adduct Formation

Differentiating acidities in different solvents

Which of the solvents could be used to differentiate the acidities of HCl (pka =-6) and HBr (pka = -9) Look at the acid base discrimination table for a variety of solvents. The only solvents for which the table covers the range -6 to -9 is methanoic acid.

OxoAcids
OpE(OH)q pKas of these acids are largely controlled by the number of O on E ( The ox. No. of E) Pauling 1.) pKa = 8-5p

e.g. H-O-Cl P(OH)3O pka(expt) 7.2 2.1 Pauling 8-5(0)=8 8-5(1) =3

S(OH)2O2 -2.0 8-5(2) = -2

2.) Successive pkas increase by approx.5 pka units H3PO4 / H2PO4expt pKa (2.1) Pauling (3) H2PO4-/ HPO32expt pKa (7.4) Pauling (8) HPO42- / PO43expt pKa (12.7) Pauling (13)

Anhydrous Oxides
Non-metal Oxides give acidic solutions in H2O SO3 = H2SO4 CO2 = H2CO3 Metal Oxides give basic solutions in H2O Na2O = 2 Na+ + 2OHAmphoteric Oxides react with acids and bases BeO + 2OH- + H2O == Be(OH)42BeO + 2H3O+ === Be2+ + 2 H2O Amphoteric Oxides ( with relatively large charge/size ratios) e.g. Al2O3, ZnO, SnO and SnO2

Hard and Soft Acids and Bases (HSAB)

The Hard/Soft Acid Base Principle

In some cases it is possible to accurately predict the way in which an ambident nucleophile will react. Hard Bases (nucleophiles) Soft Bases (nucleophiles) Hard Acids (electrophiles) (high Soft Acids (electrophiles) Donor atoms have high electronegativity (low HOMO) and low polarizability and are hard to oxidize. They hold their valence electrons tightly. Donor atoms have low electronegativity (high HOMO) and high polarizability and are easy to oxidize. They hold their valence electrons loosely. Possess small acceptor atoms, have high positive charge and do not contain unshared electron pairs in their valence shells. They have low polarizability and high electronegativity LUMO). Possess large acceptor atoms, have low positive charge and contain unshared pairs of electrons (p or d) in their valence shells. They have high polarizability and low electronegativity (low LUMO)

n.b The HSAB principle is not a theory but a statement of experimental facts.

Pearson, R.G, Songstad, J.Amer.Chem.Soc., 1967, 89, 1827

Pearsons Principle

Sample Problem
Asoft: B hard + Bsoft ==== Asoft: Bsoft + B hard

Hg(OH2)22+ + 2 SEt2 ==Hg(SEt2)2 + H2O lies to right F3B: NH3 + PMe3 == F3B: PMe3 + NH3 lies to left

MO Theory - Illustrative Examples

is faster than HO Br Br

HO

H-OH2

CH2=CH2 Br Br

is faster than CH2=CH2 H-OH2

OH- is a hard nucleophile, the charge is situated on oxygen (which is small and highly electronegative) and therefore reacts quickly with the hard electrophile such as the proton. Alkenes are very soft uncharged nucleophiles with high HOMOs, they react most easily with Br2 which is a soft electrophile possessing a low energy LUMO.

Enolate Reactivity Orbital vs. Charge Control

O (1) R R' But (2) R R' O R R' O Et3O R R' R R' CH3 OEt O CH3Br R R' O

(1) shows a soft-soft molecular orbital controlled reaction, this gives rise to bond formation at carbon (which has the largest HOMO coefficient) orbital control. (2) shows a hard-hard charge-controlled process. The largest quantity of charge density resides on the oxygen atom and the new bond is formed at oxygen under charge control.

Effect of The Leaving Group

OEt Et-X OEt

OEt O charge control

Et-X

Et OEt orbital control O O

The aceto-acetate anion is soft due to charge delocalisation over several atoms. The predominant product with the soft alkyl halide results in C-alkylation (orbital control). Variation of leaving group X leads to different product ratios i.e increasing the electronegativity of X increases the proportion of charge control.

Table 2
X= C:O alkylation CF3SO365:35 Ts85:15

Br98.5:1.5

I100:0

Ambident Nucleophiles -The Influence of Reaction Mechanism

OEt O Cl OEt

SN1 O O O O

O Et OEt Et-I SN2 O O OEt

SN1 mechanism- the nucleophile attacks a hard oxygen ion SN2 mechanism- the nucleophile attacks the carbon atom of a molecule which is a softer acid. The more electronegative atom of an ambident nucleophile is harder than the less electronegative atom, therefore moving from an SN1 like to SN2 like mechanism means that the ambident nucleophile is more likely to attack via its less electronegative (softer) atom.

Lewis Acids

Consider,

NC

CN

d+
CN R

Ag

NC

Alkyl halides are soft electrophiles in SN2 reactions and therefore react with the soft carbon anion of cyanide leading to the nitrile product. Addition of lewis acids (Ag+, Hg2+, Zn2+) assists the leaving halide ion. This gives rise to a development of charge on the carbon atom undergoing substitution (more SN1 like in character). Carbonium ions are hard and this causes cyanide to react via the harder nitrogen atom leading to isocyanides.

Alkylation of 2-Hydroxypyridine

EtI K+ N O N O N Et 73% EtI Ag+ N O N O N 80% OEt O

K+ counterion does not coordinate to I leaving group closely therefore reaction is via SN2 TS alkylation at soft N atom. Ag+ is able to coordinate effectively to I leaving group therefore reaction is via hard SN1 TS alkylation at hard O atom

Me-I alkylation, even in the presence of silver still gives 74% N-Me product. Et-I allows a greater amount of carbonium SN1 character to form than Me-I (due to Et-I better ability to stabilise charge).

MeI, DMF Ag+ N O N O N 12% OMe N Me 74% O

Absolute Hardness

Hard/Soft Acid Base PrincipleMolecular Orbital Theory

Hard acid LUMO

Hard acid (high LUMO)/ hard base (low HOMO)interaction is an ionic interaction.

Ionic interaction

Hard base HOMO

Soft acid LUMO Soft base HOMO E Covalent interaction

Soft acid (low LUMO) and soft base (high HOMO) interactions have the orbitals closer in energy which gives covalent bonding.