CHEM 313: Inorganic Structure and Bonding II (Holger Kleinke)

Prerequisite: CHEM 212

Textbooks. Housecroft, Sharpe, Inorganic Chemistry, 2007;

Miessler, Tarr, Inorganic Chemistry, 2004;
Huheey Keiter,
Huheey, Keiter Keiter,
Keiter Inorganic Chemistry,
Chemistry 1993;
West, Basic Solid State Chemistry, 1999.
Lectures. Tuesday and Thursday, 10:00 - 11:20, PHY 313.
Office hours. Wednesday, 9:00 - 10:00 a.m., C2-067.
Evaluation. Assignments (10%), one 75 minute mid-term
evaluation
l ti (30% each),
h) one 2.5
2 5 hour
h final
fi l (60%)
(60%).

Class home page: http://kleinke.uwaterloo.ca/313

Backup: http://www.science.uwaterloo.ca/~kleinke/313
1

CHEM 313: Inorganic Structure and Bonding II (Holger Kleinke)

Prerequisite: CHEM 212

CHEM 212

● Atoms, orbitals, and periodicity

● Geometric structure and localized bonding models

● Symmetry and group theory

● Valence Bond and Molecular Orbital theory

1
Acid/Base concepts and different solvents

Lewis

A Lewis acid is an electron pair acceptor.

acceptor

A Lewis base is an electron pair donor.

The Global Definition:

- incorporates all of the above ideas
- and provides a criterion for relating acid/base properties to electronic
structure.
structure

Acidity: The positive character of a species that is decreased by a

reaction with a base.

Basicity: The negative character of a species that is decreased by a

reaction with an acid. 3

Proton Transfer Equilibria in Water

Conjugate Acids and Bases

HSO4-(aq) + OH-(aq) H2O(l) + SO42-(aq)

acid base conjugate conjugate
acid base

PO43-(aq) + H2O(l) HPO42-(aq) + OH-(aq)

base acid conjugate conjugate
acid base
4

2
Strong and Weak Acids and Bases

Strong and Weak Acids and Bases

3
 Distribution Diagram for the forms of Phosphoric Acid

Solvent Levelling

1. Acids that are weak in water may appear strong in a solvent that is a more
effective proton acceptor, and vice versa.

2. Bases that are weak in water may appear strong in a more strongly proton-
donating solvent.

Levelling Effect – all stronger acids are brought down to

the acidity of H3O+

4
 Solvent Levelling
Consider (qualitatively) the pH of different pH = - log [H3O+]
acids and bases in aqueous solution.
14 CASE
-2 (a)
10 M KOH, KOEt, KNH2, BuLi

10-2 M ammonia
(b)
-2
10 M pyridine

pH 7
10-2 M phenol (c)

10-2 M HOAc (d)

10-2 M H2SO4, HClO4, HSO3CF3
0

(a) strong bases are leveled to OH- (b) weak bases are differentiated
9
(c) weak acids are differentiated (d) strong acids are leveled to H3O+

The same solutes in liquid ammonia as solvent:

2 NH3 (l) NH4+(am) + NH2-(am) pKam = 27

27

10-2 M KNH2, BuLi

10-2 M KOEt

10-2 M KOH

13.5

Pam = -log[NH4+]
10-2 M H2O (an acid in NH3!)

10-2 M phenol
10-2 M H2SO4, HClO4, HOAc
10
0

5
 Sulfuric acid as the solvent:

2 H2SO4 H3SO4+ + HSO4- pKH2SO4 = 4

4
10-2 M H2O,
O NH3,...
-2
10 M HOAc is a base!

2
10-2 M HClO4 is a weak acid!
pH2SO4 = -log[H3SO4+]

11

The Acid-Base Discrimination Window

for various Solvents

12

6
Aqua Acids

13

Hydroxoacids Oxoacids

14

7
 15

Lewis Acid-Base Reactions

A Lewis acid is an electron pair acceptor.
A Lewis base is an electron pair donor.

Lewis Acids and Bases of the s-block Elements

16

8
 5-coordinate Si atoms: TBP geometry
SiF5-, RSiF4-, [Si(C6H5)(OC6H4O)2]- (trigonal bipramid)

17

Group 15 Lewis Acids

F F
F F + H2F
F Sb F + 2 HF Sb
F F
F F F

Superacid: a mixture (usually consisting a strong Brønsted acid and a

strong Lewis acid) that is capable of protonating most organic compounds.

SbF5 + 2 HSO3F FSO3SbF5- + H2SO3F+

superacid

18

9
 Acidity of Superacids

Acid Ho
Sulfuric acid H2SO4 -11.9
Hydrofluoric acid HF -11.0
Perchloric acid HClO4 -13.0
Fluorosulfonic acid HSO3F -15.6
Trifluoromethanesulfonic HSO3CF3 -14.6
acid (triflic acid)
Magic Acid HSO3F-SbF5 -21 to -25
(depending on concentration)
Fluoroantimonic acid HF-SbF5 -21 to -28
(depending on concentration)

Hammett acidity function

[ BH  ]
H o  pK BH   log
[ B]
19

Group 15 Lewis Bases – “Super Bases” or Proton Sponges

NMe2 NMe2 NMe2 Me2N

Me Me Me2N NMe2
C C P P
Me N N Me Me2N N N NMe2 Me2N N N NMe2

pKBH+ = 12.34 pKBH+ = 29.9

-methyl groups provide a steric hindrance to

rotation about the bond between the ring
g carbon
M
Me M
Me
Me N H N Me and nitrogen.
-repulsion of the lone pairs on the nitrogen atoms
destabilize the “free base”

20

10
 Group 16 Lewis Acids and Bases

SO2 is a Lewis acid in the presence of tertiary amines.

SO2 is a Lewis base in the presence of SbF5 (O-donor).
SO2 is a Lewis base in the presence of Ru(II) (S-donor).

21

Hard and Soft Acids and Bases

Hard acids bond in the order:

I- < Br- < Cl- < F-

Soft acids bond in the order:

F- < Cl- < Br- < I-

Hard acids tend to bind to hard bases

Soft acids tend to bind to soft bases

22

11
 General rule of thumb:
- small cations (not easily polarized) are hard and form complexes
with small anions.
- large cations are more polarizable and are soft. 23

Name Structure Bp (oC) Dipole Dielectric

Moment Constant
Water HOH 100 1.85 80

Methanol CH3OH 68 1.70 33

Ethanol CH3CH2OH 78 1.69 24.3

Acetic acid CH3COOH 118 1.74 6.15

Acetone O
56 2.88 20.7
C
H3C CH3
Tetrahydrofuran 1.63 7.52
66
O

Ethyl acetate CH3COOEt 78 1.78 6.02

Acetonitrile CH3CN 81 3.92 36.6

Dimethylformamide O
153 3.82 38.3
(DMF) H N(CH3)2
Dimethyl Sulfoxide
(DMSO) O
S
189 3.96 47.2
H3C CH3
Hexane
CH3(CH2)4CH3 69 2.02

Benzene 80 0 2.28

Diethyl Ether Et2O 35 1.15 4.34

Methylene CH2Cl2 40 1.60 9.08

Chloride
24
Carbon CCl4 76 0 2.24
Tetrachloride

12
 Liquid ammonia (NH3)

- Non-aqueous ionizing solvent.

- Liquid range: -77 oC to -33 oC .

- Most striking property is its ability to dissolve alkali metals

metals.
Dilute solutions are very deep blue, concentrated ones metallic, coppery.

Solvated Electron (an example of a particle in a 3-dimensional box)

in H2O max = 800 nm

in NH3 max = 1500 nm

Na  Na+ (am) + e– (am)

- These solutions are conducting and strongly reducing!

25

Hydrogen fluoride (HF)

- boils at 19.5 oC
- acidic solvent
- good solvent for ionic substances
- highly reactive and toxic
- difficult to handle (polytetrafluoroethylene reaction vessels required)

Tetrahydrofuran (THF)
- non-aqueous solvent
- weak hard base
- boils at 66 oC
- purified by distilling from sodium/benzophenone
- widely used in the preparation of organometallic compounds
26

13
 Some Lewis Basic Solvents
O O
O
H H S CH3
H3C CH3 H N

CH3

O O
R R R H R-NH2 CH3CN

O CH3 O H CH3

S O S + NH3 S N H + O S

O CH3 O H CH3

H H H

O H N + H3O+ H N + 2 H2O
H H
H H
27

14