Main Group Chemistry

Mohammed Bakir
Department of Chemistry
University of the West Indies-Mona
Campus
 Preface

 The notes are under continuous revision, therefore

students are advised to attend lectures and tutorials
and participate in the learning process note taking
and problem solving.
 Some figures in these notes were taken from
different website and all are acknowledged. I will
try to make a list of all websites used and I
apologize for any missed site.
 Evaluation
 Students in this course will be evaluated based on the following:
 Laboratory work 20%
 In-course tests* 20%
 Final Examination 60%

 Due to the descriptive nature of this course and above evaluation

procedure as set by the university, students are advised to review the
course material regularly and pay close attention to the final examination.

 * Thursday February 16, 2006. Venue TBA.

 Thursday March 30, 2006. Venue TBA.
 Reading Materials
 Textbook and Reading Material
 F. A. Cotton & G. Wilkinson-Advanced
Inorganic Chemistry, Wiley
 F. A. Cotton, G. Wilkinson & P. L. gaus-
Basic Inorganic Chemistry, 2nd Edition,
Wiley
 N. N. Greenwood & A. Earnshaw,
Chemistry of the Elements,
Butterworth/Heineman
 B. Douglas, D. H. McDaniel, Concepts
& Models in Inorganic Chemistry,
Wiley.
 Course Outline
 The Chemistry of Hydrogen and Hydrides

 Occurrence and History.

 Preparation of Hydrogen
 Hydrogen Isotopes
 Chemical Reactions of Hydrogen
 Compounds containing Hydrogen
 The Hydrogen Bond
 Uses of Hydrogen

 Oxygen and Oxides

 Molecular oxygen and its properties

 Coordination and compounds of oxygen
 Stability of oxidation states of oxides in main groups
 Acid-base behavior of oxides
 Oxides of groups 13 and 14: structure and applications
 Important ternary oxides- ferroelectrics (perovskites),
superconducting and phosphor ceramics
 Course Outline
 Halogens and Halides

 Molecular properties of halogens

 Stability of halides in various oxidation states
 Lewis acidity of p-block halides
 Structure and reactivity of p-block halides
 Interhalogen compounds- their preparation, structures and
stabilities
 Oxo-acids and their salts.

 Organometallic Chemistry of Main Group Elements

 Classification of organometallic compounds

 Formation of M-C bonds and their stability to hydrolysis and
oxidation
 Structure and properties of lower alkyls of group 1 metals,
beryllium and boron
 Synthesis, structure and reactions of Grignard reagents
 Properties and uses of group 14 organometallic compounds
1H 2He

3Li 4Be Periodic Table of the Elements 5B 6 C 7 N 8O 9F 10 Ne

11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar

19
K 20
Ca 21
Sc 22
Ti 23
V 24
Cr 25
Mn 26
Fe 26
Co 28
Ni 20
Cu 30
Zn 31
Ga 32
Ge 33
As 34
Se 35
Br 36
Kr

37 Rb 38 Sr 39 Y 40 Zr 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 Pt 47 Ag 48 Cd 49 In 50 Sn 51 Sb 52 Te 53 I 54 Xe

55
Cs 56
Ba 57
La† 58
Hf 59
Ta 60
W 70
Re 71
Os 72
Ir 73
Pd 74
Au 75
Hg 76
Tl 77
Pb 78
Bi 79
Po 80
At 81
Rn

87
Fr 88
Ra 89
Ac†† 104
Rf 105
Ha 106 107 108 109

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

58
Ce 59
Pr 60
Nd 61
Pm 62
Sm 63
Eu 64
Gd 65
Tb 66
Dy 67
Ho 68
Er 69
Tm 70
Yb 71
Lu
† Lanthanide
Series 90
Th 91
Pa 92
U 93
Np 94
Pu 95
Am 96
Cm 97
Bk 98
Cf 99
Es 100
Fm 101
Md 102
No 103
Lr
†† Actinide Series
 Hydrogen Chemistry
Hydrogen: Greek- hydro -waterand genes -forming

1
1.0079 H

The lightest element and has only proton and one electron and
it has no neutron.

All other elements were originally made from hydrogen atoms or

other elements that were originally made from hydrogen
atoms.

Reference: Inorganic Chemistry, Shriver

& Atkins 3rd Edition, Oxford University
Press, 1999.
 Hydrogen History
 1671 - Robert Boyle dissolved iron fillings in dilute
hydrochloric acid and reported that the ‘fumes’ given off
were highly flammable.
 1766 - Discovered and isolated by Henry Cavendish in
1766. 1781-H2+O2+ ED → H2O
 1781 – Named Hydrogen by Antoine Lavoisier.
 1789- van Troostwijk & Deiman-Electrolysis of water-
 1898 - James Dewar produced the first liquid hydrogen.
 1900 - the first ‘Zeppelin =Airship’ made its flight filled
with hydrogen. Hindenburg 1937
 1909-The pH scale by P. L. Sørensen
 1923-J. N. Brønsted defined an acid as a proton donor.
 1931 - Harold Urey discovered deuterium.
 1947-LiAlH4 prepared by H. I. Schlesinger-Chicago
University
 1954-Detonation of H-Bomb on Bikini Atoll
 1960’s Super acid (BF3-HF)G. A. Olah.. Nobel 1994 H-Bomb 1952
 1978- H. C. Brown Nobel Prize, Purdue University,
Hydroboration
 1984-First Stable T.M. dihydrogen compound discoved by
G. Kubas
 1996 - Metallic hydrogen was prepared
1900-1930’s German war machine
1891 water splitting
Poul la Cour -Danish
 Why Hydrogen?
Hydrogen is a Part of Life
H2O , NH3, MeOH ….

The first hydrogen refueling station

Reykjavík, Iceland in April 2003.

DaimlerChrysler fuel cell buses went

into public use in nine cities across
the European Union in 2004.
Hydrogen “Town Gas” Once Lit
Hydrogen Economy America (1850-1900)
 Some Uses Hydrogen
 Selected uses of hydrogen:

 Food ... to hydrogenate liquid oils (e.g. soybean, fish, cottonseed and corn) converting them to
semisolid materials such as shortenings, margarine and peanut butter.
 Chemical processing ... primarily to manufacture ammonia (nitrogen fixation), hydrochloric acid
and methanol, but also to hydrogenate non-edible oils for soaps, insulation, plastics, ointments and
other specialty chemicals.
 Metal production and fabrication ... to serve as a protective atmosphere in high-temperature
operations such as stainless steel manufacturing; commonly mixed with argon for welding austenitic
stainless. Also used to support plasma welding and cutting operations.
 Pharmaceuticals ... to produce sorbitol (sugar alcohol) used in cosmetics, adhesives, surfactants, and
vitamins A and C.
 Aerospace ... to fuel spacecraft, but also to power life-support systems and computers, yielding
drinkable water as a by-product.
 Electronics ... to create specially controlled atmospheres in the production of semiconductor
circuits.
 Petroleum Recovery and Refinery ... to enhance performance of petroleum products by removing
organic sulfur from crude oil, as well as to convert heavy crude to lighter, easier to refine, and more
marketable products. Hydrogen's use in reformulated gas products helps refiners meet Clean Air
Act requirements.
 Power Generation ... to serve as a heat transfer medium for cooling high speed turbine generators.
Also used to react with oxygen in the cooling water system of boiling water nuclear reactors to
suppress stress corrosion cracking in the cooling system.
 Fuel Cells ... used as a fuel to power fuel cell generators that create electricity through an
electrochemical process in combination with oxygen.
 Occurrence
 Hydrogen (hydrogen atoms) is the most abundant element in the universe (90%
of all atoms and ¾ of total mass), followed by Helium.

 Hydrogen is found in the stars and plays an important role in powering the
Universe through interstellar proton-proton reaction* and carbon-nitrogen
cycle** .

41H→4He + 2e+ + 2ν e Q = 26.72 MeV @ T > 107K

Q=Energy evolved
(νe is neutrino)
41H + 12 C→4He + 12 C+ 2e+ + 2ν e Q = 26.72 MeV @ T >1.6x107

 Hydrogen is the third (after oxygen and silicon) most abundant element in earth.

 Despite its simplicity and abundance, hydrogen doesn't occur naturally as a gas
on the Earth—it's always combined with other elements.
 Hydrogen
1
1.0079 H Nuclear spin = ½
Electron Spin = ± ½

Electronic configuration
1s1 (H.)
1s1 - e- → 1s0 (H+)
1s1 + e- → 1s2 (H-)
 Location in the Periodic Table

1 2 17 18
1
1.008 H 1s1 ↔ 1
1.008 H 1s1 2
He 1s2
3
Li ….2s1 4
Be 9
F 2s22p7 10
Ne 2s2sp6

11
Na….3s1 12
Mg 17
Cl
19
K…. 4s1 20
Ca 35
Br
37
Rb …5s1 38
Sr 53
I
55
Cs …6s1 56
Ba 85
At
87
Fr … 7s1 88
Ra
 Summary
 Despite its position on top of Group I, it is not really
part of this group:

 It is a gas and not a metal.

 It does not react with water. Selected
 Far more electronegative than the alkali Electronegativities
(Pauling
Scale)
 Electronegativity is the tendency of an atom F 4.0
in a molecule to attract electrons. Cl 3.0
O 3.5
 Electronegativity is useful in predicting the
N 3.0
general chemical behavior of an element.
S 2.5
 In general large difference in C 2.5
electronegativity between two elements H 2.1
leads to the formation of ions and small B 2.0
difference in electronegativity leads to
sharing of electrons. Na 0.9
 Nuclear Properties
Hydorgen Isotopes*
Isotope Symbol Natural ½-life Nuclear Spin NMR
Abundance, % Sensitivity

Protium** 1
H 99.985 Stable ½ 1.000

Deuterium***,12H, D 0.01 Stable 1 0.0097

†

Tritium†† 1
3
H, T 10-17 Radio-active 1/2 1.21
β -emitter†
12.4 year

•*Have the largest isotope effect of all elements because of the largest mass differences.
•**The dominant isotope.

•*** Natural hydrogen contains ~ 0.002% D.

•† β -radiation ≡ 0-1 e
 Isotope Effects
Hydorgen Isotopes*
Isotope H2 D2 H2 O D2O

Noiling -252.81 -249.7 100.00 101.42

point/C

Mean Bond 436.0 443.3 463.5 470.9

Enthalpy
(kJmol-1 )

See Deuterium and Tritium Isotopes – synthesis and applications.

Major used in spectroscopy as tracers to confirm the presence or absence of
certain isotopes.
 Vibrational Transitions
∆ E = hν = (h/2π ) (k/µ )1/2

Where k is the stretching force constant, and µ is

the reduced mass
µ = m1m2/(m1+m2),
i.e. 1/µ = 1/m1 + 1/m2 for m1 & m2

Units of k = force units (dyne cm-1 )

ν Used interchangeably for frequency (sec-1 ) or wavenumber (cm-
)
1
 Vibrational Transitions
 M is important in determining the frequency
of vibration.
 If in H-C , H is replaced with D, there will be
negligible change in the force constant but
appreciable change in the reduced mass.
 ν (C-H) and ν (C-D) vibrations are
proportional to
 [12x1/(12+1)]-1/2 and [12x1/(12+2)]-1/2
 Therefore ν (C-H) is 1.3 to 1.4 times ν (C-D).
 Force Constant k
 Its magnitude hints to the strength of bond
e.g. 13-18x105 dyne cm-1 triple bond
8-12x105 dyne cm-1 triple bond
<8x105 dyne cm-1 single bond.
 IR bands 4000-600 cm-1 (stretching and bending
vibrations)
 >2900 cm-1 due to H bound to a low-mass atom.
 This frequency decreases as the H-X bond becomes
weaker and the atomic weight of X increases.
 Triple bond bond stretches occur in the range 2000-
2700 cm-1 .
 Double bond stretches occur 1500-1700 cm-1 .
 Metal-ligand vibrations <400 cm-1 .
Nuclear Equations and Selected
Nuclide Symbols
Atomicweight
Atomic# X

Proton 1
1 H 1
1 P
Neutron 1
0n
Electron 0
-1 e or 0
-1 β
Positron 0
1 e or 0
1 β
Gamma photon 0
γ
0

238
92
U →234
90
Th +
42He
 1
H-1H Fusion Reactions 1
Η
 Interstellar Thermonuclear Proton-proton reaction*
1
Η

41H→4He + 2e+ + 2Ve Q = 26.72 MeV @ T > 107K Q=Energy evolved

n

 1
H + 1H → 2H + e+ + νe + 0.42 MeV ; νe is neutrino, hydrogen-hydrogen fusion
 e+ + e- → 2γ + 1.02 MeV positron-electron annihilates 1
Η
 2
H + 1H → 3He + γ + 5.49 MeV deuterium-hydrogen fusion
 3
He +3He → 4He + 1H + 1H + 12.86 MeV

ν
 For H-Bomb a fission reaction (atomic bomb) e +
is used to initiate proton-proton reaction

 Carbon-nitrogen-oxygen cycle**

41H + 12
C→4He + 12 C+ 2e+ + 2Ve Q = 26.72 MeV @ T >1.6x107 3
Ηe
12
C + 1H → 13 N + γ
13
N → 13 C + e+ + νe
13
C + 1H → 14 N + γ
14
N + 1H → 15 O + γ
15
O → 15 N + e+ + νe
15
N + 1H → 12 C + 4He
γ
Nucleogenesis
 The Chemistry of Hydrogen Atom is dominated by the following:

 Loss of an electron to for a proton H+,

H(g) → H+ (g) + e- ∆ H = 569 kJ/mole = 13.59 eV

1s1 – e- → 1s0
Owning the high charge density, i.e. high charge/size ratio the resulting
proton has no existence on its own and is always associated with other
species, i.e. solvated.

H+(g) + nH2O (l) → H3O+ (aq) ∆ H = -1090 kJ/mol

 Sharing of electrons with other elements to form covalent compounds.

See hydrides of hyperelectronic elements, F, O, N and others, e.g. HF, H2O, NH3

 Acceptance of an electron to for a hydride ion, H-

H + e - → H- ∆ H = 72 kJ/mole
The hydride formation is ~ favorable and several hydride of Groups 1 & 2
such as NaH, CaH2 are known.
1s1 + e- → 1s2
1H 2He

3Li 4Be Periodic Table of the Elements 5B 6 C 7 N 8O 9F 10 Ne

11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar

19
K 20
Ca 21
Sc 22
Ti 23
V 24
Cr 25
Mn 26
Fe 26
Co 28
Ni 20
Cu 30
Zn 31
Ga 32
Ge 33
As 34
Se 35
Br 36
Kr

37 Rb 38 Sr 39 Y 40 Zr 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 Pt 47 Ag 48 Cd 49 In 50 Sn 51 Sb 52 Te 53 I 54 Xe

55
Cs 56
Ba 57
La† 58
Hf 59
Ta 60
W 70
Re 71
Os 72
Ir 73
Pd 74
Au 75
Hg 76
Tl 77
Pb 78
Bi 79
Po 80
At 81
Rn

87
Fr 88
Ra 89
Ac†† 104
Rf 105
Ha 106 107 108 109

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

58
Ce 59
Pr 60
Nd 61
Pm 62
Sm 63
Eu 64
Gd 65
Tb 66
Dy 67
Ho 68
Er 69
Tm 70
Yb 71
Lu
† Lanthanide
Series 90
Th 91
Pa 92
U 93
Np 94
Pu 95
Am 96
Cm 97
Bk 98
Cf 99
Es 100
Fm 101
Md 102
No 103
Lr
†† Actinide Series
 The Chemistry of Hydrogen is dominated by the following

 Formation of non-stoichiometric hydrides with

Transition metals (TM) and other less electropositive
elements, e.g. ReH9, MHx

M + x/2 H2 → MHx
 The Chemistry of Hydrogen is dominated by the following:
 Formation of multi-centered hydrogen bridged bonds, e.g.

2e`s/3-centered bonds as in B2H6 and other TM hydrides

that contain M-H-B bonds.
-
H H H CO
CO
CO
CO

B B OC Cr H Cr CO
OC
H OC
H H CO
CO

M' M
H
H M M
M M M
M M H
M M H
M M H M M
M M
M
M M

Fasten ≡ Hapto ≡ µ n
µ 2
µ 3
µ 4
µ 5
µ 6

 Participation in Hydrogen Bonding of the type X-H…Y.

 3-center 2-electron Bond
 e.g. H3+ Ψ(B1) - Ψ(B2)
Ψ3

Ψ(B1) Ψ(B2)

Ψ2 Ψ(H)

Ψ(B1) + Ψ(B2)

 [H H-H]+ ↔ [H+ H-H] Ψ1

Propose a bonding scheme for H3+.

 3-center 2-electron Bond
 e.g. B2H6

H H H H H H H
B B
B B
H H H
H H

BH2(sp3) 1e- 2H (1e-/atom) BH3(sp3)0e-

 5B 1s2 2s22p1
 B is sp2 hybridized (BH3) = 6e- does not satisfy the octet rule, i.e.
electron deficient
 i.e. 2s12px12py2pz0
 BH3 dimerize to satisfy the octet rule by sharing electrons between
different atoms.
 B is sp3 in (B2H6)
 Selected Chemistry of Hydrogen
 Atomic Hydrogen
Bond Dissociation Energies (kJmol-1 ) of
X-Y

H-H* + 436
Cl-Cl +242
C-H +414
N-H +391
*
Strong bond requires energy (electric
discharge) of catalyst (metal atoms e.g.
Pt, Ni) for dissociation.

 Atomic hydrogen is very reactive and is a

good reducing agent.
 Atomic Hydrogen
 Formation of atomic hydrogen
 Electrical discharge (ED)
H2 + heat → 2H.
e.g. H2 + O2 → N.R.
H2 + ½ O2 + ED → H2O
 Catalyst-metal particle, transition metal compounds
 H2 + M0 → M..H (M = Ni, Pt, Pd ….)
H-H H H
 H2 + → →
Adsorption Dissociation
 Reactions of atomic hydrogen-Hydrogenation of
unsaturated compounds- e.g. vegetable oil.
 Hydrogenation
H2 RHC=CHR’

RHC=CHR’ H RHCH-CHR’
H H

RHCH-CHHR’

Propose a mechanism for the hydrogenation and

isomerization of 2-propen-1-ol (CH3CH=CHOH)
on a Pt surface?
 Dihydrogen (H2)
 Properties-colorless, odorless, tasteless, highly flammable gas
(b.p. -252.5 C = 20.3 K).
 Electronic States
 Two electronic states are possible
 Ortho H2 in which the nuclear spin of each hydrogen atom is aligned parallel to
the other atom, i.e multiplicity = 3.
 Para H2 in which the nuclear spin of hydrogen atoms are aligned in opposite
direction , i.e. multiplicity = 1

o-H2 → p-H2 conversion is exothermic & is forbidden thermally without

complete dissociation of H2.
A catalyst such as TM atoms of Pd, Pt and metal oxides such as Fe2O3.
H H
3:1 mixtures of o-/p- are possible.
M + H2 M
 Preparation of
Hydrogen
 Reaction of electropositive metals with water
 e.g.

 2 Na + 2 H2O → H2+ 2 Na++ 2 OH-

 Ca + 2 H2O→ H2+ Ca2+ + 2 OH-

 In the lab: reaction of Fe or Zn with acids

 Zn + 2 H3O+ → H2+ Zn2+ + 2 H2O

 Synthesis
 Steam Reforming of Hydrocarbons

CH4 + H2O → CO + 3H2 Ni catalyst at ~800 °C

Synthesis gas: mCO/nH2 mixture

Uses of synthesis gas (syngas)

mCO + nH2 → Hydrocarbons, e.g. methanol, glycol,

wax, gasoline
catalyst
 Synthesis

 Thermal Cracking of Hydrocarbons

e.g. CnHn+2 → CnHn + H2 Heat

 Coal gasification
~1000 0C
C + H2O → CO + H2 (water gas reaction)

400 0C
CO + H2O → CO2 + H2 (water gas shift reaction)
Fe2O3 or Cr2O3

 Hydrolysis of hydrides of group 1 &2

CaH2 + 2H2O → Ca(OH)2 + 2H2

Hydride anion (H-) is a very strong base and hence react with proton to form dihydrogen.
 Preparation of Hydrogen

 Electrolysis-

2H2O (l) + e`s → 2H2(g) + O2(g) on inert electrode, e.g. Pt

electrode

Write balance half-reactions for the electrolysis of water?

Show balanced half-reactions for the electrolysis of water.

2NaCl(l) + 2Hg + e`s → 2NaHg(l) + Cl2(g)

2NaHg (l) +H2O(l) → 2H2(g) + 2Hg(l)
 Hydrogen Fuel Cell
Swiss scientist
C. Friedrich Schönbein in 1838 Membrane

Pt-black on Graphite, ANODE Electrolyte CATHODE, Pt-black on Graphite

-
e.g. H3PO4
+
H2 O2

H2 H+ ½ O2 + 2H+ + 2e- → H2O

e- e-

e-
External circuit
Pt-black is dispersed Pt-particle
nH2PtCl6 + 2nH2 → (Pt0)n + 6nHCl
Fuel Cell
 Fuel Cell

lic
o vota
t
Pho
cel l

O2

H2 O
Electrolyzer H2 Fuel Cell

H2 O
 Semiconductors

----
Conduction Band

+ + + +
Valence Band

p-type n-type

p-type semiconductor: semiconductor e.g. Si doped with electron

deficient impurity e.g. B or Ga.
n- type semiconductor: semiconductor e.g. Si doped with electron
rich impurity e.g. As.
 Reactions of Molecular Hydrogen
(H2)
 Reaction with O2
H2(g) + O2(g) → N.R
2H2(g) + O2(g) + ED → 2H2O(l)
 Reaction with H2O
H2(g) + H2O(l) → N.R.
 Reaction with Halogens
H2(g) + F2(g) → 2HF(g)
 Reaction with acids
H2(g) + H+(l) → N.R.
 Reaction with bases
H2(g) + OH-(l) → N.R.
 Hydrides (H-); s-block (Groups I & II) hydrides
 Preparation

 Reaction of a powerful reducing metal (alkali and alkaline earth metals) with
hydrogen gas.
M + ½ H2(g) → M+-H- (ionic)

 The chemistry of ionic H- is similar to the chemistry of halogens (X-).

 ½ Cl2 → Cl(g) ∆ H = +121 kJ/mol

 Cl(g) + e-→ Cl-(g) ∆ H = -369 kJ/mol
 ½ Cl2 (g) + e- → Cl-(g) ∆ H = -248 kJ/mol

 ½ H2 → H(g) ∆ H = +217.5 kJ/mol

 H(g) + e-→ H-(g) ∆ H = -69 kJ/mol
 ½ H2 (g) + e- → H-(g) ∆ H = 148.5 kJ/mol

 ∴ Formation of Cl- is more favorable than H-.

 Metals with electronegativity < 1.2 form ionic hydrides.
∆ Hf of M- (kJ/mol) of H & other elements
½ M2(g) → M-(g)

H* +146.4

Na +38

F -351.5

Cl -251.0

Unstable in water
H- + H2O → H2 + OH-
 Reactions of H-
 Binary Ionic hydrides are usually used as reducing agents in synthetic
chemistry, but they are too strongly basic and reactive to be used in
pure form.

 Hydrides of lesser reactivity e.g. LiAlH4 and NaBH4

LiH + AlCl3 → LiAlH4 Schlesinger, 1947

NaH + BF3 → NaBH4 Brown & Schlesinger

are more commonly used especially if the reaction can be carried out in
water or organic solvents

 With acids-H- is a strong base.

 NaH + CH3COCH3 → Na+[CH3COCH2]- + H2

 NaH + H2O → NaOH + H2

 MH + H+ → M+ + H2
 Covalent Hydrides
 The electrons in the bond are shared between M &
H.
 The electronegativity of the element ~2.1 and varies
from ~2.5-1.5.
Electronegativity

H 2.1
P 2.2
 Bond Spolarity 2.5 depends on electronegativity
differences between M &H and varies from δ + (e.g.
S-H) to δ - (e.g. B-H and Ga-H)
 Hydrides
1 2 13 14 15 16 17
LiH BeH2 (BH3)2, …. CH4 NH3 H2O HF
NaH MgH2 (AlH3)n SnH4 PH3 H2S HCl

KH CaH2 GaH3 GeH4 AsH3 H2Se HBr

RbH SrH2 InH3 SnH4 SbH3 H2Te HI

Ionic Ionic Covalent Covalent

Hydrides
E +H - Eδ +Hδ - E-H Hδ +Eδ -

Red Blue White

Selected hydrides of p-block elements that contain M-H
covalent Bonds*,**

13 14 15 16 17
B2H6 CnH2n+2 NH3 H2 O HF
CnH2n
CnH2n-2
(AlH3)n SinH2n+2 (n ≤ 8) PH3 H2 S HCl

P2 H 4 H2Sn
GenH2n+2 (n ≤ 9) AsH3 H2Se HBr

SnH4 SbH3 H2Te HI

* Polarity varies depending on electronegativity differences of M-H
bond.
** Group 13 hydrides are electron deficient-
 Classification of covalent
hydrides
 Electron-precise hydrides – all electrons of the
central atom are engaged in bonds. E.g. MH4
where M is a group 14 metal (C, Sn, Si).
 Electron-deficient hydrides – insufficient
electrons to satisfy the octet rule—share
electrons to reach the Noble Gas (NG)
configuration. E.g. BH3 and AlH3
 Electron-rich hydrides – more electron pairs
on the central atom than are needed for bond
formation. E.g. NH3
 Synthesis of p-block Hydrides
 Direct Combination of elements
2H2 + O2 → 2H2O Heat (∆ ), Light (hν )or Electric Discharge (ED)
H2 +Cl2→ 2HCl

 Reduction of halides or oxides

SiCl4 + LiAlH4 → SiH4 + LiAlCl4

 Hydrolysis
Ca3P2 + 6H2O → 2PH3 + 3Ca(OH)2
Ca3N2 + 6H2O → 2PH3 + 3Ca(OH)2

Note: P3- phosphide very strong base & N3- nitride very strong base

 Interconversion of hydrides
nGeH4 → Ge2H6 + Ge3H8 + higher hydrides
Covalent Hydrides of Group 14

Heat of formation of MH4, kJmol-1 *

CH4 -75
SiH4 +33.5
GeH4 +92
SnH4 +163
* Stability decrease down the
group, i.e. metastable, SnH4
decompose >300 C to Sn + H2
 Reactions of Covalent Hydrides
 Reducing agents

SiH4 + 8O2 → SiO2 + 2H2O fast

 Condensation Reactions

M=O + NH2R → M=NR + H2O

M=O + H2N-NH2 → M≡ N + H2O
 Synthesis of T.M. Hydrides
 Action of Hydride Sources on Metal Complexes
 Hydride sources Aldehydes, Sugars, Alcohols, Water, NH4+,
BH4-, AlH4-…
e.g. trans-PtCl2(PEt3)2 → trans-PtClH(PEt3)2
FeI2(CO)4 + NaBH4 → FeH2(CO)4 (THF solvent)

 Reactions Involving Molecular Hydrogen

e.g. RhCl(PPh3)3+ H2 ↔ RhCl(H)2(PPh3)3
Wilkinson Catalyst - Nobel 1973 (see C21J catalytic hydrogenation of
alkene)
WMe3 + 3PMe3 + H2 → WH4(PMe3)3
 Synthesis of T.M. Hydrides
 Reaction of Hydrogen Compounds HX= HCl or
HSiCl3…. Oxidative Addition
trans-IrICl(CO)(PPh3)2 + HSiCl3 ↔ IrIII Cl(H)(SiCl3)(CO)(PPh3)2
(Vaska’s Compound)

trans-PtII Cl2(PEt3)2 + HCl ↔ PtIV Cl3H(PEt3)2

 Reduction
THF H+
Mn2(CO)10 + Na/Hg → Na[Mn(CO)5] → H[Mn(CO)5]
H2C CH2

H2C CH2
O
THF

KReVII O4 + K → K2ReVII H9 in damp (1,2-diaminoethane)

 Molecular Hydrogen Compounds
 e.g. Ru(H)2(H2)(PPh3)2, Ir(H2)(CO)(PPh3)2, W(η 2-H2)
(CO)3(Pi-Pr3)3

LnM + H2 ↔ LnM(H2) ↔ LnM(H)2

M(CO)3(PPri3)3 + H2 → M(η 2-H2)(CO)3(PPri3)3

H3C H
OC
H3C CH3 H

P M = Mo or W
P(iPr)3 W P(iPr)3
H3C CH3
CO
H3C CO

Greg Kubas 1984, Los Alamos National Laboratory,

PPri3 = tri-isopropylphosphine ν H-H = 2690 cm-1 , ν HD = 2360 cm-1
dH-H = 0.84 Å (dHH in free H2 = 0.74 Å)
 Molecular Hydrogen Compounds

Cr(CO)6 + H2 → Co(η 2-H2)(CO)5 + CO (hν liq. Xe)

trans-[FeClH(dppe)2 + H2 + NaBPh4 → [FeH(η 2-H2)(dppe)2] + + BPh4- + NaCl

H
H R H
P
P P
P R =
R R
Fe H
H
P P
H H
Dppe = diphenypphosphinoethane
Hydrides of Transition Metals Bonding
H H
H
LnM LnM LnM
H H
L = Ligand, M with d =0-2 dihydrogen complex H
dihydride complex
3-centered-2-electron bond

In most cases M-H bond is formed and not dihydrogen formation.

H
H
M
H
M H

σ *

σ ( Η 2 ) →empty metal orbital dm → empty σ * (backbonding)

H2 act as 2e- s donor

Μ Μ ←Η 2 Η 2
 Reactions of T.M. Hydrides
 Acidity-
 e.g. HCo(CO)4 & HV(CO)6 strong acids

LnMH ↔ LnM- + H+
Cp2ReH + LiBu → Li[ReCp2] + BuH

 Hydrogen Migration Reactions

LnMH + R2C=CR’2 → LnM-Cα R2-Cβ ( Η ) R2’
LnMH + CO → LnM-C( −Η ) ( = Ο )

 Elimination Reactions
LnMH + LmM’R → LnM-M’Lm +RH
LnMH + CO → LnM-C( −Η ) ( = Ο )
Non-covalent Hydrogen Bonds

Proteinexplorer.org
 Non-covalent Hydrogen Bonds
 The non-covalent secondary interactions between covalently
bonded hydrogen atom and other atoms is called a hydrogen
bond (see below)

Xd- -Hd+ …Yd-

H-donor → H-acceptor
Where X is an atom that forms a covalent bond with H, and
Y is an atom that forms non-covalent bond with H. In the
old literature X and Y referred to highly electronegative
elements such as Cl, F, O, and N and in recent years X and
Y refer to any atoms that may participate in the formation
of weak non-covalent interactions.
The hydrogen bond is a special case of
dipole forces.
 Non-covalent Hydrogen Bonds
 Non-covalent Hydrogen Bonds have bond enthalpies of +4-40
kJmol-1 is significantly weaker than the bond enthalpies of
classic (normal) 2e-/2-centered covalent hydrogen bond of the
type H-X such as HCl (∆ H = +431 kJ/mol) and is a stronger
than weak van der Waals forces between molecules.

 X-H…Y → X-H + Y ∆ H < 15 kJ/mol weak

∆ H = 15-40 kJ/mol intermediate
∆ H > 40 kJ/mol strong
 e.g. O-H…O

 If d(O…O) = 3.0-2.8 Å weak

 If d(O…O) = 2.8-2.6 Å stronger with ∆ H = 15-40 kJ/mol

 ∆ H = 0 kJ/mol if d(X…Y) = van der Waals distance.

Bond Length
 Non-covalent Hydrogen Bonds

 Applications

 Self-assembly of molecules to form supramolecular

structures important in the recently developed area of
nano-materials to form devices based and biomolecules see
self-assembly of DNA and proteins.

 Stabilization of solid state structures.

 Molecular sensors- solvent-solute interactions

 Examples of Non-Covalent Hydrogen Bonds

H δ + H
H
 Water- O
H
O
δ -

N H
O
N
CH
H δ -

CH C C C
NH
C
HC N H N
C N
NH C
H
N
 HF + F → [F….H-F]
- - O
H

 NH4F H
+
δ +
δ
F
-
H

H N H
H
H
 Non-covalent Hydrogen Bonds
 Boiling Point Differences-for spherical non polar
molecules
 SnH4>GeH4>SiH4>CH4
 Xe>Kr>Ar>Ne>He
 The boiling point differences here is explained based on
weak van deer Walls & dipole-dipole interactions; i.e.
polarizability of atoms or molecules-the higher the
polarizability (large size) the higher is the boiling point.
 The dipole is proportional to α 2/r6 where α is the
polarizability and r is distance between atoms or
molecules. The polarizability increases with the increase in
size. δ −
δ −

δ +
δ +
 Non-covalent Hydrogen Bonds
 Boiling Point Differences For MH3, MH2, and MH of
Groups 15, 16 & 17 the following trend was noted:
NH3>SbH3>AsH3>PH3 N O F
H2O>H2Te>H2Se>H2S P S Cl
HF>HI>HBr>HCl As Se Br
Sb Te I

The boiling point differences here is explained in terms of

a combination of weak non-covalent interactions. In the
case of HF, H2O, and NH3 hydrogen bonding is very
effective and for the rest polarizability is more effective
than H-bonding alone.
 Non-covalent Hydrogen Bonds
 Factors that affect the strength of H-Bond of the type ~ 10-
40kJ/mole
M1δ —Hδ +….M2
 1. Electrostatic attraction
M1δ − — Hδ +….M2δ -
 2. Delocalization (or covalent bonding) effect-the electrostatic
attraction in 1 will polarize, i.e. pull the electron clouds in M2 towards
the H-M1 region of space.
 3. Electron cloud repulsion-the ∑van deer Waals for H & O is
2.6 Å and in O…H the bond distance ~ 1.6 Å. Thus e--e-
repulsion will occur when the electronic clouds of O1-H &
O2 start to overlap.
 London (van der Waals) forces-their effect is relatively
small ~2-4 kJmol-1/each pair of non-contacting atoms or
molecules.
 Detection of Non-covalent Hydrogen Bonds
 Spectroscopic
 IR & Raman
 The ν (X-H) stretching frequency of X-H…Y shifts to lower
wavenumber (λ − = 1/λ ) and the width and intensity of the band
increases ~ 10 fold.
∆ E = (h/2π )ν = (h/2π )(k/µ )1/2 where k =
force constant and µ = reduced mass.
M1 µ =
1/M2
1/m1+1/m2
 The δ (X-H) bending frequency shifts to higher wave number.
 NMR
 Proton of X-H of X-H…Y shifts to lower field (more positive value)
when hydrogen bonded compared to non-hydrogen bonded because of
the decrease in the diamagnetic shielding of the proton.
 Diffraction
 X-ray- packing of molecules reveal X-H…Y bonds.
 Neutron Diffraction-may locate the location of H atom and its
surroundings.
 Properties of Non-Covalent Hydrogen Bonds

 Non-covalent hydrogen bonds of the type X-H..Y are not

symmetrical. The hydrogen atom is closer to X than Y.
 Non-covalent hydrogen bonds of the type X-H…Y are
linear or slightly bent to maximize the Y…H interaction
and minimize X-Y repulsion.
 The valence angle θ (see below) is in the range 100-140°.

 Hydrogen atoms in XNCHB H are normally 2-coordinate and

Y
examples of 3-coordinate (bifurcated) and 4-coordinate
θ R
(trifurcated) are known.
 Covalent Hydrides of Group 14
 Synthesis - reduction of their halides with LiAlH4
SiCl4 + LiAlH4 → SiH4
Si2Cl6 + LiAlH4 → Si2H6
Si3Cl8 + LiAlH4 → Si3H8

 Properties
 Thermal decomposition
Si5H12 → 2(SiH)x + Si2H6 + SiH4
 Reactions with alkali metals
GeH4 + K → KGeH3 + ½ H2
 Reactions of Anions-
CH3Cl + KGeH3 → CH3GeH3 + KCl
Mn(CO)5Br + KGeH3 → (CO)5MnGeH3 + KCl
 Covalent Hydrides of Group 16

Physical data on Group 16 hydrides, MH2

Element <HMH d(M-H) ,Å K1* K2**
O 104.5 0.96
S 92 1.32 10-7 10-15
Se 91 1.47 1.3x10-4 10-11
Te 89.5 1.69 2.3x10-3 2x10-11
* K1 of MH2(aq) → MH- + H+ (aq)
** K2 of MH-(aq) → M2- + H+ (aq)
 Covalent Hydrides of Group 16

 S- forms rings and cyclic hydrides of sulfur are

known
 Na + S → Na2Sx
 Na2Sx + HCl → H2Sn distillation H2Sn n = 2-6
 2H2Sx + SyCl2 → 2HCl + H2S2x+y
 Covalent Hydrides of Group 15
 Synthesis of MH3 Derivatives
MX3 + LiAlH4 → MH3 (except Bi), X a halide.
 Acid hydrolysis of alloys containing Group 15 elements give
hydrides of different types, NH3, M2H4 (P, As, Sb) & M3H5 (P, As),
 For p light sensitive, thermally unstable linear PnHn+z (n = 9 and
monocyclic (PnHn) and polyciclic derivatives are obtained.

 N2 + 3H2 ↔ 2NH3, at 500 C, 200-300 atm, ∆ H(25) = -92.4 kJ/mol,

∆ S negative
 In nature Molybdenum enzyme nitrogenaze is used.
 Tritium††
 Synthesis & reactions of tritiated compounds -
 2 T2 + O2 → 2T2O Pd as catalyst, or ED (redox reaction)

 2 T2 + CuO → T2O + Cu
 LiH + T2 → LiT + HT @ 350 °C (exchange reaction)
 LiBH4 + T2 → LiBH3T + HT @ 200 °C
 2AgCl + T2 → Ag + 2TCl @ 700 °C (redox nreaction)
 Br2 + T2 → 2TBr hν or ∆
 M + x/2T2 → MTx heat
 Deuterium†
 Synthesis-of deuterium as D2O from fractional distillation of water, electrolysis and isotope exchange,
i.e. exchange of normal H2O

H2O(l) + HSD(g) ↔ HOD(l) + H2S(g) K ~ 1.01 at 25 C.

H2O(l) + HD(g) ↔ HOD(l) + H2(g)
2 D2 + O2 → 2D2O Energy-electric discharge
2 D2 + CuO → D2O + Cu
 Uses

 D2O is used as moderator for nuclear reactors to reduce the energy of fast fission neutron to
thermal energy as it has a lower capture cross section for neutrons than does protium hence does
not reduce the neutron flux significantly.
 Solvent in NMR.
 Mechanistic and spectroscopic studies-labeling studies or tagging. ν (M-H) vs. ν (M-D).

 Synthesis of deuterated compounds.

3CaC2 + 6D2O → 3 DC≡ CD + 3Ca(OD)2 (Hydrolysis reaction)
3 DC≡ CD + 3Ca(OD)2 → C6D6 catalyst
SO3 + D2O → D2SO4 (Addition reaction)
Li3N + 3D2O → ND3 + 3LiOD (Hydrolysis of metal nitrides ≡ N3- )
Mg3N2 + D2O → ND3 (Hydrolysis of metal nitrides ≡ N3- )
Na + D2O → D2 + Na2O (Reduction of D2O)
LiC6H5 + D2O → C6H3D (Hydrolysis of organometallics)
 Tritium††
 Most sensitive NMR nucleus
 Synthesis-
 Neutron capture

14
7N + 10n → 31T + 12 6C
14
7 N + 11H → 31T + fragments
6
3 Li + 10n → 31T + 42He
2
1 H + 21H → 31T + 11H

 Uses
 Energy source from fusion reaction
3
1 T + 21D → 42He (3.5 MeV) + 10n (14.1 eV)
 Synthesis of tritiated compounds
(see synthesis of deuterated compounds)
 The Chemistry of Proton (H++)
 In the gas phase the reaction is highly endothermic, i.e.
requires a large amount of energy.
H(g) -e- → H+(g) ∆ H = + 569 kJ/mol=13.59eV
Endothermic
 Hydrogen compounds generate protons only in a media
that can solvate the proton since energy is required for
bond rupture. Protic acids.

 In aqueous media it is solvated to form H3O+

hydroxonium ion ≡ hydronium ≡ oxonium.
 H(g) + nH2O(l) → H3O+(aq) ∆ H = - 1090 kJ/mol-1 Exothermic
 H(g) + e- → H-(g) ∆ H0 = 72 kJ/mol
 The Chemistry of Proton (H++)
 The IE of hydrogen is higher than that of alkali metals
 The loss of e- from hydrogen forms a very unstable highly charged species
(radius ~10-5 Å) which cannot exist except in vacuum. In solution it
undergoes solvation

+217.5 kJ +1310 kJ -1172 kJ

 ½ H2 (g) → H(g) → H+(g) → H+(aq)
1st IE (kJ/mol) of H & other
elements
M(g) → M+(g) + e-
 ½ H2 → H+ (aq) ∆ H0 = +355.5 kJ/mol) H +1310
 more endothermic than the alkali metals Li +518.8
+159 kJ +518.8 kJ -514.6 kJ
Na +493.8
 Li(s) → Li(g) → Li +
(g) → Li +
(aq) F +1682
Cl +1255
 Li(s) → Li ∆ H = 163.2 kJ/mol
+
(aq)
0
C +1088
 Problem Set #3
 Describe the three methods for the synthesis and reactions of dihydrogen. Use appropriate chemical
equations to illustrate your answer.
 Differentiate between the electronic states of dihydrogen and give three methods for the interconversion
between states.
 Predict the products of the following reactions
1. K2O + D2O 2. CO2 + D2O
3. BF3 + D- 4. NCl3 + LiAlD4
5. SO3 + D2O 6. BT3 + NaT
7. P4O10 + H2O 8. H2SO4 + NaCl
9. P(CH3)2Cl + LiAlH4 10. Na2S + HCl

 Describe three procedures illustrated with examples for the synthesis of covalent hydraides of main
group elements of Group 13-17.
 Describe three procedures for the synthesis of main group hydrides and show three reactions of main
group hydrides.
 Show the mode(s) of binding of dihydrogen to transition metal compounds and give appropriate
examples of transition metal compounds that contain dihydrogen as a ligand.
 Describe procedures illustrated with examples for the synthesis of transition metals hydrides.
 Differentiate between covalent hydrogen bonds and non-covalent hydrogen bonds.
 What are the factors that influence the strength of covalent and non-covalent hydrogen bonds?
 Give three procedures illustrated with examples for the synthesis of transition metal hydrides and
dihydrogen compounds.
 Show using appropriate example how you may detect and determine the presence of hydrogen bonds.
 Oxygen Chemistry
Oxygen: Greek- oxus or oxys (sharp, acid)and geinomai or genes
(former)-acidformer

8
15.9994 O 1s22s22p4

The most abundant element in the universe and

has eight proton, eight electron and eight
neutron.

Oxygen is an important component of air,

produced by plants during photosynthesis and is
necessary for aerobic respiration in animals.
 The Group 16 Elements (Chalcogens)
Metalic Properties Element Oxidation States Catination*

Non-metal 8
O -2→+2** Not favored

Non-metal 16
S +6 Favored

Semi-conductor 34
Se +4 Exist

Semi-conductor 52
Te Low favored Exist

Metal 84
Po*** +2→+4 -

*
Formation of rings and chains.
** e.g. OF2
Radioactive 209 83 Bi + n,γ → 210 83 Bi → 210 Po +0-1 β
***
( α -active t1/2 =
138.4d)
Location in the Periodic
Table Selected
Electronegativities
(Pauling Scale)

F 4.0
Cl 3.0
O 3.5
N 3.0
S 2.5
C 2.5
H 2.1
B 2.0
Na 0.9
 History
 <1771- prepared by many individuals but were not able to isolate it or recognize it as an
element.
 In 1770, G.E. Stahl, a German physician - all inflammable objects contained a material
substance that he called "phlogiston," from a Greek word meaning "to set on fire."
 1771 Carl Wilhelm Scheele (Swedish pharmacist) discovered Oxygen called it ‘fire air’
was not immediately recognized.
 1772 - Joseph Black (Scottish chemist), and his student, Daniel Rutherford- a living
creature gives up phlogiston while breathing and when placed in air that is already
saturated with phlogiston, can no longer breathe and must die.
 1774 Joseph Priestley independent discovery & confirmed oxygen.
 1774 Antoine Laurent Lavoisier – oxygen.
 1848 - Faraday while he was investigating the magnetic susceptibility of matter, he
discovered that oxygen could be drawn into a magnetic field (paramagnetic).
 1950 - Paul Hersch developed electrochemical oxygen sensor.

 Scheele Joseph Priestley Antoine L. Lavoisier Benjamin Franklin Cartoon of Priestley calling for the head
Radical Thinker & wife Marie-Ann Paulze
(Through a conscious revolution, became the father of modern chemistry) of King George III.
(Law degree at the Collège Mazarin)
 Why Oxygen?
 Oxygen is a part of life - supports all life on this planet and is essential to combustion as well as respiration

 Photosynthesis Respiration Agriculture Environment

 Chemicals, H2O2 Zeolites

 Selected Uses of
Oxygen
 Essential for many important industrial and biological processes that may include:

 Oxidizer (only fluorine having a higher electronegativity) used in rocket propulsion and
manufacturing disinfectant, pharmaceuticals, etc….
 Medicine & Biological life support- Respiration - oxygen supplementation, gas
poisoning, and anesthetic when mixed with nitrous oxide, ether vapor, etc..
 Oxygen is essential for life takes part in processes of combustion & respiration.
 Oxygen is used in welding.
 Metalloragy- melting, mining, refining and manufacture of steel, other metals and
manufacture of stone and glass products.
 Recreational - mild euphoric, has a history of recreational use often mixed with nitrous
oxide to promote a kind of analgesic effect.
 Manufacture of chemicals by controlled oxidation
 Occurrence
 Oxygen is the most abundant element in the Universe originated by green-
plant photosynthesis.
chlorophyl/enzyme
H2O + CO2 + hv ↔ O2 + {CH2O} ∆ H = +/- 469 kJmol-1

 Oxygen comprises about 46.7 % of earth’s crust, 87% by weight of the

oceans (as H2O) and 20% of the atmosphere of Earth (as O2, molecular
oxygen, or O3, ozone).

 Oxygen compounds, particularly metal oxides, silicates (SiO44− ), and

carbonates (CO32− ), are commonly found in rocks and soil.

 Frozen water is a common solid on the outer planets and comets. The ice
caps of Mars are made of frozen carbon dioxide.

 Oxygen compounds are found throughout the universe and the spectrum of
oxygen is often seen in stars (see carbon-nitrogen-oxygen cycle in 1H-1H
fusion.
 Forms of oxygen
 Molecular – O2, O3 and O4 (allotropes)
 Atomic- highly reactive
 Ionic- oxides O2-, peroxides O22-,
superoxides O2-, …. (see group I and II
oxides).
 Molecular (covalent) compound of
oxygen – neutral (e.g. SiO2, OsO4,
CO2..) & ionic (e.g. SO42-, CO32-, NO3-, …)
 Molecular oxygen

 Oxygen is a colorless, odorless gas and at standard pressure,

oxygen liquefies to a pale blue liquid which boils at -183.0 ºC.
Solid oxygen melts at -218.8 ºC. Oxygen is sparingly soluble in
water & slightly heavier than air.

Liquid O2
 Chemical Synthesis of O2
 From water
 Electrolysis (see synthesis of hydrogen).

 Chemical oxidation of water

2H2O + 2Cl2 → 4HCl + O2

 From oxides
 Thermal decomposition

e.g. 2HgO → 2Hg + O2

2BaO2 → 2 BaO + O2
2KMnO4 → K2MnO4 + MnO2 + O2

 chemical decomposition

e.g. MnO2 + 2H2SO4 → 2MnSO4 + 2H2O + O2

 Catalytic decomposition of peroxides

2H2O2 → 2H2O + O2 (MnO2 catalyst)
 Industrial Production
 Fractional distillation of liquefied air @-183
°C (O2) and @ -196 °C .

Air
Gas Volume %

N2 78.1
O2 20.9
Ar 0.93
CO2 0.035
 Molecular Orbitals of O2
σ ∗ 2p σ ∗ 2p σ ∗ 2p

π ∗ 2p π ∗ 2p π ∗ 2p

2p4 2p4 2p4

2p 4

π π π 2p
2p 2p

σ σ σ 2p
2p 2p

σ ∗ 2s σ ∗ 2s σ ∗ 2s
2s2 2s2 2s2
2s2

σ σ σ 2s
2s 2s

σ ∗ 1s σ ∗ 1s σ ∗ 1s
1s2 1s2 1s2 1s2
σ σ σ 1s
1s 1s

Ground state O2 Triplet Excited State Singlet Exited State Singlet

S=1 0 0
Multiplicity = 2S+1 = 3 1 1
Stability stable reactive reactive
 O2 Diradical Triplet (3O2)
LUMO σ ∗ 2p
HOMO π ∗ 2p

2p4 2p4

π 2p

σ 2p
σ ∗ 2s
2s2 2s2
σ 2s
The two anti-bonding electrons have the same spin (parallel)
Bond order = ½(# bonding electrons - # anti-bonding
electrons)
= 1/2 (6-2) = 2
Multiplicity = 2S + 1 , where S = Total spin = ∑s
S = ½+1/2 = 1 and Multiplicity = 2(1) + 1 = 3
 Chemistry of Triplet
 3O
oxygen
2give stereo mixed addition
products.
 Selected reactions of
oxygen
 Triplet O - Ground State:
2 2

 Metals ions - Metal ions are radicals

themselves, so can react with dioxygen.
 e.g.

 Fe2+ + O2 ↔ [ Fe2+ - O2 ↔ Fe3+- O2-.] ↔ Fe3+ + O2-. (superoxide)

 O2 & Haemoglobin

 Active site metalloprophyrin

 e.g. prophyrin &
metalloprophyrin
H H
H H R CH C
R CH C
R
R C C
C C
C C N C
N C H
H HC
HC C
C H N C H
N H C H M CH
C
C CH H C N
H C H N
C
C C
H C C H
C H N
N R C
R C C C
C C
R
R C HC
C HC
H H
H H
O2 Binding site
 Selected reactions of
 Triplet O - Ground State:oxygen
2

 Autoxidation of organic molecules to produce peroxides. In this free

radical reaction, several reactions occur, including

RH → R.
(Initiation)
R. + O2 → ROO.
(Propagation)
ROO. + RH → R. + ROOH
(Propagation)
R. + R. → R--R (Termination)
ROO. + ROO. → ROOR + O2
(Termination)
ROO. + R. → ROOR (Termination)
The initiation step above occurs mostly at C atoms which can produce the
most stable free radicals (allylic, benzylic position, and 3o > 2o >> 10
carbons). Hence unsaturated fatty acids are extra reactive at the
methylene C that separate the double bonds.
 Single Oxygen (1O2)

t ½ = 10-4 s 10-9 s

hν / sensitizer (e.g. dye)

-hν (633 &703 nm)

Chemoluminescence

1
O2(⇅) + 1O2(⇅) → 3O2(⇈) + 3O2(⇊) ∆ H = -184 kJmol-1 (λ = 633 nm)
1
O2(↑)(↓) → 3O2(⇈) ∆ H = -184 kJmol-1 (λ = 703 nm)
Chemical Synthesis of Singlet
Oxygen
 Cl2 + 2OH- → ClO- + Cl- + H2O

ClO- -HCl
 H-O-O-H → H-O-O-Cl → 1O=O
-OH- (peroxohypochloric acid)
 Selected Reactions of 1O2
 1O acts as a nucleophile, i.e. pair of electron
2
donor- electron rich
3
O2 → 1O2 (hν /sensitizer)
 Ene Reaction H3C CH3
H3C CH3
+ O O
H3C
CH2
H3C CH3 O
 1,4-cycloaddition OH

CH3 CH3

h v / s e n s i t i z e r
+ O O O
O

 1,2-cycloaddition
CH3 CH3

H3 C H3C
H3 C
CH2 + O O
H 3C O + H2 C O
H 3C
O O
H3C

 http://www.medicine.uiowa.edu/ESR/education/FreeRadicalSp01/Paper%201/Zhaol-
 http://class.fst.ohio-state.edu/fst821/lec/singlet2pdf.pdf
 http://daecr1.harvard.edu/pdf/smnr_2005_Nagorny_Pavel.Pdf
 Di-oxygen metal compounds
 Metal-dioxygen compounds

 http://www.res.titech.ac.jp/~smart/research/subject(e).html
 http://www.iuac.org/publications/pac/1995/pdf/6702x0241.pdf
 Di-oxygen metal compounds
 The HOMO have π -symmetry, thus dioxygen bind to metal
species in angular or sideways using one of its filled π (2p)
orbitals as 2e donor-backbonding from metal d to π *(2P)
(H 5C6)3P O

Pt[P(C6H5)3]4 + O2 → Pt
O
(H 5C6)3P

(H 5C6)3P
OC O
Ir
IrCl(CO)[P(C6H5)3]2 + O2 → Cl O
O
(H 5C6)3P
Ir
Vaska’s complex O

O2 is π -donor-π -acceptor

Conditions: Mn+ ,n = 0, 1, 2,
 Metal-dioxygen
compounds
 O2 + M → M---O2
 M---O2 + S → SOx

 M = transition metal (catalyst or enzyme)

 S = substrate
5 6 7 8 9 10 11
V Cr Mn Fe Co Ni Cu
Nb Mo Tc Ru Rh Pd Ag
Ta W re Os Ir Pt Au
Binding modes of dioxygen in transition metal compounds
TDNL-M
O TDNL-M
O
TDNL-M
O O
O O
M-TDNL

η2- η1-
µ−η1,η1-

µ- bridging

TDNL-M O
O
O O TDNL-M
TDNL-M M-TDNL M-TDNL

M-TDNL O O

µ-η1,η2- µ-η2,η2- bis-µ-oxo-

R

N
R
N R
TDNL = Tridentate nitrogen ligand, e.g.
B
N N
N
N
R

R R

N N

N
 Comparison of 3O2 & 1O2
3
O2 O2
1

Energy level 0 22.5 Kcal/mol

Nature Diradical Non-radical,

Electrophilic
Reaction Radical Electron Rich
Compound
 Ozone

O
O
O O
O O

 Ozone Greek – ozein - to smell

 In standard state, a pale blue, highly poisonous gas with a strong odor.
 Liquid ozone is a deep blue and strongly magnetic.
 Ozone is much more active chemically than ordinary oxygen and is a better oxidizing agent.
 Ozone is used in purifying water, sterilizing air, and bleaching foods.
 At low concentrations, ozone can be relatively pleasant. (The characteristic clean odor associated with
summer thunderstorms is due to the formation of small amounts of O3)
 Exposure to O3 at higher concentrations leads to coughing, rapid beating of the heart, chest pain, and
general body pain. At concentrations above 1 ppm, ozone is toxic.
 Ozone Depletion

 http://www.atm.ch.cam.ac.uk/tour/part3.ht
ml
 Formation of O3

 Solar (stratosphere)
(
hν <200 nm
O2 → 2O
O + O2 → O3
Upper atmosphere, water treatment

 Chemical

 3O2(g) + ED → 2O3(g) ∆ Hf =143 kJmol-1

 E.g. ED = photcopies, motors, lightning
 Ozone

 Oxygen ↔ ozone

 http://www.cotf.edu/ete/modules/ozone/ozatmo
Formation of O3

hν <420 nm
NO2 → NO + O
O + O2 → O3
 Selected Reactions of O3
 Redox reactions
2Fe2+ + 2H++ O3 → 2Fe3+ + H2O + O2
 Ozonolysis of alkenes

H3C CH3 O O
H3C
H3C -O
C C + C C CH3 2
O3 C O
H3C O
H3C CH3 CH3 H3C
 Ozone Hole Depletion
2O2 O3
Chlorofluorocarbons
hν
e.g. CCl3F
hν
.CCl2F + Cl. ClO
Paul J. Crutzen, Mario J.
Molina and F. Sherwood
O3 O2
Rowland , Nobel 1995

NO2 ClONO
hν NO

Many radicals such as OH, NO, Br, Cl… cause ozone depletion
 Chloro-flurocarbons (CFC) Repalcements
 Cl2 + hn → 2Cl.

 Hydrochlorofluorocarbons are considered interim replacements for CFCs. Although

more ozone-friendly than CFCs, they still destroy some ozone.

 Hydrofluorocarbons and fluorocarbons are ozone-safe, but some have high global
warming potential.

 In some cases, ammonia (NH3), butane (C4H10 ), or pentane (C5H12 ) can be suitable
substitutes for CFCs.

 http://www.cotf.edu/ete/modules/ozone/ozatmo2.html
 http://www.meteorology.monash.edu.au/info/factmar98.pdf
 Redox chemistry of O2
σ ∗ 2p σ ∗ 2p σ ∗ 2p σ ∗ 2p
π ∗ 2p π ∗ 2p π ∗ 2p π ∗ 2p π ∗ 2p

π 2p π π π π
2p 2p 2p 2p
σ 2p σ σ σ σ
2p 2p 2p 2p

σ ∗ 2s σ ∗ 2s σ ∗ 2s σ ∗ 2s σ ∗ 2s

σ 2s σ σ σ σ
2s 2s 2s 2s

σ ∗ 1s σ ∗ 1s σ ∗ 1s σ ∗ 1s σ ∗ 1s

σ 1s σ σ σ σ
1s 1s 1s 1s
O2+ Ground state O2 Superoxide, O2- Peroxide, O22- 2 oxide, O2-
S = 1/2 1 1/2 0 0
Multiplicity = 2S+1
2 3 2 1 1
Bond order
2.5 2 1.5 1 0
O2 ± ne ↔ O2±n
 Redox Chemistry of O2

.. .. .. ..
 :O=O: + e- → [:O
.. -. O:] = O2-. Superoxide

.. .. .. ..
 :O=O: + 2e- → [:O
.. - ..O:] = O22- peroxide
.. .. ..
 :O=O: + 4e- → 2 [ :O:
.. ] O2- oxide
Properties of O2
d(O-O) , Å Dissociation Bond Order Magnetic Properties
Energy
(kjmol-1)

O2+ 1.12 623 2.5 Paramagnetic

O2 1.21 490 2.0 Paramagnetic
O2- 1.32 1.5 Paramagnetic
O22- 1.49 398 1.0 Diamagnetic
 Main Group Oxides: Ionic vs Covalent

 With the exception of a few Nobel gas Selected

elements such as Xe, oxygen forms oxides Electronegativities
(Pauling
with all elements in the periodic table. Scale)
 If ∆ EN > 1.5 (see EN table) where EN = F 4.0
electronegativity the oxide is ionic. Cl 3.0
O 3.5
 If ∆ EN < 1.5 (see EN table) the oxide is
N 3.0
covalent.
S 2.5
C 2.5
H 2.1
B 2.0
Na 0.9
 Main Group Oxides
Increasing covalent & acidic character
Increasing ionic & basic character

1 2 13 14 15 16 17
Li2O BeO B2O3 CO2 N2O5
Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7
K2O CaO Ga2O3 GeO2 As2O5 SeO3 Br2O5

Rb2O SrO In2O3 SnO2 Sb2O5 TeO3 I2O5

Cs2O BaO2 Th2O3 PbO2 Bi2O5

Ionic Amphto Covalent
Basic eric Acidic
 http://depts.washington.edu/chemcrs/bulkdisk/
http://depts.washington.edu/chemcrs/bulkdisk
 Acid-base Behavior of MG-

oxides
Elements with low Electronegativity (EN) form ionic oxides →
basic
O2- + H2O → 2OH-
O2- + 2H+ → H2O

 Elements with high EN form covalent oxides → acidic

SO3 + H2O → H2SO4 → H+ + HSO4-

SO3 + 2OH+ → SO42- + H2O

 Elements with intermediate EN form amphteric oxides →

react with acids and bases

Al2O3 + 6H+ → 2Al3+ + 3H2O

Al2O3 + 2OH- + 3H2O → 2Al(OH)4-
 Synthesis of oxides

 Direct reaction of element with O2

 For group I & II metals

M + O2 → M2O + M2O2 + MO2 (M group 1)

 Formation of Oxides (M2O), peroxides (M2O2) and superoxides

(MO2) where M = group I elements in this case are obtained
from the direct reaction of metals with oxygen depending on the
ratio of metal to oxygen.
Hydrolysis of goup I & II oxides

 M2O + H2O → 2M+ + 2OH- oxides (O2- )

 M2O2 + 2H2O → 2M+ + 2OH- + H2O2

peroxide (O22- )

 2MO2 + 2H2O → O2 + 2M+ +2OH- + H2O2

superoxide (O2-1 )

M = Group I metal in this case

 Acid-base Behavior of main group
oxides
 Metal-oxides react with water to form

bases

e.g. BaO(s) + H2O(l) → Ba2+ (aq) + 2OH-(aq)

 Nonmetal oxides react with water to

from acidic solutions.

e.g. CO2(g) + H2O(l) → H2CO3(aq)

P4O10(s) + 6H2O(l) → 4H3PO4 (aq)
 Synthesis & Reactions of MG-oxides
 Check the following sites for reactions and preparations of
MG-oxides

http://www.physchem.co.za/Inorganic/Oxygen.htm

http://web.chemistry.gatech.edu/~wilkinson/Class_notes/spring_2004_1311_page/slides/Desc

http://www.google.com/search?q=%27synthesis+of+main+group+cov

http://chemed.chem.purdue.edu/demos/main_pages/10.
 Hydrogen Peroxides
 Why Hydrogen Peroxide?
 Selected Uses of Hydrogen Peroxides
 Multipurpose Disinfectant - Kills mold, mildew, fungi, viruses,
bacteria and other harmful biological contaminants.
 Health – toothpaste, mouthwash, shower, facial …
 Agriculture - Sprouting Seeds, House and Garden Plants,
Vegetable Soak
 Powerful Oxidizer for a variety of organic and inorganic compounds
 "green" bleaching agents for the paper and textile industries.
 Wastewater treatment.
 Hydrometallurgical processes (for example, the extraction of
uranium by oxidation)
 Bleaching agent - paper, textile, teeth and hair
 Powerful Oxidant
 Oxidant Oxidation Potential, V
Fluorine 3.0
Hydroxyl radical 2.8
Ozone 2.1
Hydrogen peroxide 1.8
Potassium permanganate 1.7
Chlorine dioxide 1.5
Chlorine 1.4

 H2O2 converts to hydroxyl radical –powerful oxidant

 Synthesis of Hydrogen
 Hydrolysis of Group I and IIPeroxides
peroxides

e.g. BaO2 + 2H2O → H2O2 + Ba(OH)2

 Nature – photolysis & acid-base conversion of O3

O3 + H2O → H2O2 + O2 hν
O3 + HO- → HO2- + O2 @ high pH
HO2- + H2O → H2O2 + HO-

 Electrolysis – aqueous solutions of sulfuric acids, of potassium bisulfate, or of

ammonium bisulfate

2HSO4-(aq) -2e- → HSO3OOSO3H

HSO3OOSO3H + H2O → 2HSO4- + H2O2

Describe the synthesis of D2O2.

 Industrial Preparation of
Hydrogen Peroxides

 Industry- I.G. Farbenindustrie

OH O

+ H2 O 2
+ O2

O
OH
Extract with H 2O & concentrate

H2 - Pd or Ni Catalyst
 Reactions of Hydrogen
Peroxide
 H2O2 is metastable and decomposes as
is metastable and decomposes
shown below
2H2O2 → 2H2O + O2 ∆ H0 = -98.2 kJmol-1
∆ G0 = -119.2 kJmol-1
(Heterogeneous (e.g. MnO2, Ag, Au or Pt) and homogenous (e.g. OH-, I-, Cu2+ or
Fe3+) enhance decomposition)
H2O2 → 2HO. (in cold, dark – catalyzed at high T and hν )

(HO. –highly reactive …. chain reactions )

 Redox Behavior of H2O2
 H2O2 exhibits amphoteric redox properties, i.e. the strength of
the oxidation is pH dependent – diversity & selectivity
 e.g. in acidic solution KI is oxidized but not in neutral solution &
MnO4- is oxidized to Mn2+ and Mn4+ at pH = 0 and 7, respectively.

2I- + H2O2 + 2H+ → I2 + 2H2O @ pH = 0

2I- + H2O2 + 2H+ → no reaction @ pH = 7

2MnO4- + 5H2O2 + 6H+ → 2 Mn2+ + 5O2 + 8H2O @ pH = 0

2MnO4- + 3H2O2 + 2H+ → 2 MnO2 + 3O2 + 4H2O @ pH = 5
 Acid-base Behavior of H2O2
 H2O2 – a stronger acid than H2O
H2O2 + H2O → HO2- + H3O pKa = 11.65 @298K
of the same order as the third Ka of H3PO4
H3O2+ + H2O → H2O2 + H3O+
 Salts of H3O2+
H2O2 + HF + MF5 → [H3O2]+[MF6]- M = Sb or As

 Reaction with base

H2O2 + NaOH → NaO2H + H2O
H2O2 + NH3 → NH4O2H + H2O
H2O2 + 2NaOH → 2NaO2 + 2H2O
 In-course test # 2
 March 30, 2006 @ 1:00 pm
 Venue : Old Dramatic Theater
 Main Group Covalent Oxides
Borates, Carbonates and Silicates

 Borate carbonate Silicate

 MG Covalent Oxides

 Synthesis: Direct reaction of element with oxygen

e.g. C(s) + O2(g) → CO2(g)

S(s) + O2(g) → SO2(g)
4P(s) + 5O2(g) → P4O10(s)
 Borate
 Why borate
 Occurrence
 Everywhere – trace amounts found in
water, soil, plants, animals and the
food we eat.
 Large amounts found in evaporated
saline lakes
 Selected Uses of Borate
 Antiseptic - minor burns, cuts or eye wash (very
diluted). It is poisonous if taken internally or inhaled,
although it is generally not considered to be much
more toxic than table salt
 Insecticide- killing cockroaches, termites, fire ants,
fleas, and many other insects. It can be used directly
in powdered form for fleas and cockroaches, or
mixed with sugar for ants. It is also a component of
many commercial insecticides.
 Food - preservative and other activities.
 Group 13 Oxides

 M2O3
 M + O2 → M2O3
 Ga2O3 + 4Ga→ Ga2O heat 700 C
 Tl2O3 → Tl2O 700 C and 115 mmHg
Group 13 Hydroxides*

B(OH)3 Acidic

Al(OH)3 Amphoteric

Ga(OH)3 Amphoteric

In(OH)3 Amphoteric

Tl(OH)3** Does not Exist

*Metallic properties (hence basicity) increase

down the group
** The oxide Tl2O3 is basic and dissolves in acids
to give Tl(III) salts.
 Boric acid, [B(OH)3]
 Synthesis
B2O3 + 3H2O → 2B(OH)3

OH O

HO B + OH- -
O B
O
H
OH H
O

Triangular Tetrahedral H

 Account for the stability of B(OH)3.

 Bonding
 In the isoelectronic series
 BO33-, CO32- & NO3-
 The short M-O bond distance is
due to π −π interaction
& increase in the order
 NO ->CO 2->BO 3-
3 3 3

 Size differences.
 Polymerization –Sol Gel Synthesis
 Sol-gel synthesis – elimination of H2O from
adjacent MOH units & formation of oxygen
bridged unit.

 e.g.

LnMOH + LnMOH → M-O-M + H2O

L = ligand & M = main group or TM element
 B-X Bond Energy
Bond ∆ H, kJmol-1
B-O 808±21
B-B 297±21
B-Si 288.3
B-C 448±
 Polymerization of Boric Acid
 B(OH)3 – linear, cyclic, 2-dimensional polymers, slimes

HO
HO O OH HO O OH

B B B B
B OH

HO OH OH O O

OH
HO O O O OH

B B B B

OH OH OH OH

HO

B O

O B O

B O B O

O B O B OH

B O B O

O B O B OH

B O B O

HO HO

n
 Polymerization of B(OH)4-
 Three dimensional solid borates – molecular sieves-
adsorbents when n >1000
OH
OH HO O
OH O
HO O -B OH B- -B OH

B- HO B- O
O
OH HO O O
HO B-

HO OH
HO OH
O O O
HO B- -B OH O

O B- -B O

O O
B- O O
O O B-

O O

HO B- -B OH

O O B- -B O
HO OH O
O O
n
 Isoelectronic relatioship
 Isoelectronic ≡ same number of
electrons
 Borosilicates &
Borophosphate
 Copolymerize NaB(OH)4 + Si(OH)4

 xNaB(OH)4 + ySi(OH)4 → Nax[(BO2)x(SiO2)y] + nH2O

 Framework anionic – used for cation exchange

 xNa[B(OH)4] + y[P(OH)4]Cl →
{(BO2)x(PO2)y} + n NaCl
 Oxides of Group 14

 Only C form multiple bonds with oxygen as C=O due to π p-π p bonding,
the other elements of the group form single bond with oxygen.

 Si-O bond is very strong bond.

 M(OH)4 M = Si, Ge are acidic and form salts with different metal ions.

 M(OH)62- M = Sn or Pb
 M-O Bond strength

M-M bond ∆ Hf0, kJmol-1

Si-Si 326
C-C 356
Si-O 799.6
C-O 336
Si-F 552
Si–H 299
Si-B 288.3

 In general, bonds with electronegative elements are stronger

with silicon than with carbon.
 Silicates
 Si-oxide- SiO2-Td of SiO44- shared by Si-O-Si bonding
 SiCl4 + 4H2O → Si(OH)4 + 4HCl
 nSi(OH)4 + heat → [SiO2]n + 2nH2O

OH

HO Si OH

OH
 Silicates
 Linear
O- O- O O -O O
Si O-
Si O Si Si
Si Si
-O O O -O
O- O O-
O
-O -O n n

O O O
Si Si Si
O O O O O O O O
Si Si Si Si
O O O O
Si Si Si Si
O O O O O O O O
 Cyclic Si
O
Si
O
Si
O
n
-O O-
O
-O Si Si O- O O O
Si Si
O O O O
Si
Si
O
-O O-
-O
O- O
-O O Si Si
O O
-O Si O
O Si Si O
O- O O
O Si
Si
Si O O- O
-O
O-
 Zeolites
 What are zeolites?
 Zeolites
 Zeolites are strictly microporous crystalline aluminosilicate
solids with structures based upon a three dimensional
polymeric framework with a general formula

Mx/n.[(SiO2)y(AlO2)x].mH2O

Non-framework cation. Framework. Sorbed phase

where M is cation with valence n

 Molecular sieves: non-crystalline

 Occurrence

 Natural – minerals

 Synthetic
 Why zeolites?
 Selected uses of zeolites
 Petrochemical cracking - catalyst
 Ion-exchange (water softening and
purification)
 Separation and removal of gases and
solvents.
 Agriculture
 Construction.
 Zeolite Structure
 Basic building block is a tetrahedron centered on either a
silicon or an aluminium atom (T) with bonds to four oxygen
atoms located at the corners.

OH
OH HO
HO
Al-
Si
OH
OH HO
HO

(HO)3Si-OH + HO-M(OH)3n → (HO)3Si-O-M(OH)3n + H2O

n = 0, -1, M=Si or Al

+ →
 Zeolite Structure
 Note: Si(IV)
Al(III)
P(V)

 SiO2 (quartz is neutral), and NaAlO2 is ionic.

 The substitution of Si(IV) by Al(III) creates an

electrical imbalance to preserve the electrical
neutrality, each [AlO4] tetrahedral needs a
balancing positive charge.
 Zeolite Structure
i.e. [SiO4]4- & [AlO4]5- Tetrahedra linked together by corner-
sharing, forming a bent oxygen-bridges.

Direct Al-O-Al linkage is not allowed in

zeolites, although know in non-zeolitic
structures such as Ca4(Al6O12)
Zeolite Structure
 Zeolite Structure
 As a direct consequence to the extension of the channel system
throughout zeolites crystals up to half of the total volume
defined by the external surface is in fact void and available to
penetration by gas phase molecules.

 The internal surface area of these zeolites will only be

accessible to fluid phase molecules which are small enough to
pass through the geometrical restrictions of the pore aperture,
i.e. molecular sieve action.

 Molecular sieve action: is the selective adsorption on the

internal surface due to size and shape of the molecule
concerned.
Zeolite Structure
 Zeolite Structure

 Si/Al Ratio

 Catalyst have high Si/Al ratio >20

 Changing the Si/Al ratio changes the cationic

content, fewer Al atoms gives zeolites with
fewer exchangeable cations.

 High silicon zeolites are hydrophobic in

character and have a greater affinity for
hydrocarbons.
 Zeolite Synthesis
 Sol-gel synthesis - hydrothermal in the range 300-450
K using Na4[SiO4] and Na[Al(OH)4]- at high pH using
alkali metal hydroxide and or organic bases. A gel
forms by a process of copolymerization of silicate and
aluminate anions, and heated in a closed vessel to give
the desired zeolites

 Silicon rich zeolites are prepared using a large

quaternary ammonium cations instead of Na+.
 Catalysis by zeolites
 Zeolites have the ability to act as catalysts for
chemical reactions which take place within the
internal cavities.

 An important class of reactions is that catalysed by

hydrogen-exchanged zeolites, whose framework-
bound protons give rise to very high acidity. This is
exploited in many organic reactions, including
crude oil cracking, isomerisation and fuel
synthesis.

 Oxidation or reduction catalysts - after metals have

been introduced into the framework. Examples are
the use of copper zeolites in NOx decomposition.

 Shape-selective catalysts due to unique

microporous nature of a particular pore system..
 Shape selective catalysis
 Reactant Selective Catalysis

 Schematic diagram of reactant shape selectivity: Rejection of branched chained hydrocarbons

 Product shape Selective Catalysis

 Schematic diagram of product shape selectivity: Para-xylene diffuses

preferentially out of the zeolite channels
 Shape selective catalysis
 Transition State Selective Catalysis

Schematic diagram of Transition State shape selectivity: only para-

xylene fits inside the channel channels
 Group 17 Elements (Halogens)
 Halogen – Greek hals ≡ salt and gennan ≡ to
form or generate, i.e. salt formers

Group 17 State @ RT Color

9
F Gas Pale yellow
17
Cl Gas Yellow-green
35
Br Liquid Orange
53
I Solid Black

84
At radioactive
 Group 17 Elements (Halogens)
Element Electronic 1st IE Covalent Ionic radius EA (kJmol- D**x2, kJmol-
Configuration (kJmol-1) radius* (Å) X-, (Å) 1) 1

F 1s22s22p5 1682 0.71 1.19 332.7 157.7

Cl [Ne]3s23p5 1255 0.99 1.67 348.5 243.5
Br [Ar]3d10 4s24p5 1142 1.14 1.82 324.5 192.9

I [Kr]4d10 5s25p5 1009 1.33 2.06 295.4 150.6

At [Xe]4f14 4d10 6s2 912 255.3 116

6p5
•Defined as ½ the bond distance in X2.
•**Dissociation Energy of X2. F2 is low because of increased repulsion of lone pairs on
adjacent fluorine atoms because of their close proximity in F2 compared to Cl2.
1H 2He

3Li 4Be Periodic Table of the Elements 5B 6 C 7 N 8O 9F 10 Ne

11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar

19
K 20
Ca 21
Sc 22
Ti 23
V 24
Cr 25
Mn 26
Fe 26
Co 28
Ni 20
Cu 30
Zn 31
Ga 32
Ge 33
As 34
Se 35
Br 36
Kr

37 Rb 38 Sr 39 Y 40 Zr 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 Pt 47 Ag 48 Cd 49 In 50 Sn 51 Sb 52 Te 53 I 54 Xe

55
Cs 56
Ba 57
La† 58
Hf 59
Ta 60
W 70
Re 71
Os 72
Ir 73
Pd 74
Au 75
Hg 76
Tl 77
Pb 78
Bi 79
Po 80
At 81
Rn

87
Fr 88
Ra 89
Ac†† 104
Rf 105
Ha 106 107 108 109

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

58
Ce 59
Pr 60
Nd 61
Pm 62
Sm 63
Eu 64
Gd 65
Tb 66
Dy 67
Ho 68
Er 69
Tm 70
Yb 71
Lu
† Lanthanide
Series 90
Th 91
Pa 92
U 93
Np 94
Pu 95
Am 96
Cm 97
Bk 98
Cf 99
Es 100
Fm 101
Md 102
No 103
Lr
†† Actinide Series
 History
 Fluorine
 1771- Carl Wilhelm
Scheele (Swedish) obtained impure hydrofluoric acid but was not able to
identify the element attached to hydrogen.
 1809 -anhydrous hydrofluoric acid was prepared & Andre´-Marie
Ampe`re (French) suggested (1811) that it was a compound of hydrogen with an

unknown element, analogous to chlorine.

 Fluorine’s toxicity caused serious health problems for several chemists. At least
two chemists—Paulin Louget and Jerome Nickles died as a direct result of
attempts to isolate fluorine.
 1886 - Henri Moissan (French) isolated the element, died at the age of 54. Nobel
1906.

 History
 Chlorine
 1772 - Scheele thought it was an oxygen-containing
substance.
 1810 - Humphry Davy had completed a careful search
for the oxygen, but, failing to find any, changed its
name from oxymuriatic acid (muriatic acid is HCl and
chlorine is an oxidation
product of HCl) to chlorine, since he was convinced
this was an element
 World War - chlorine was used as a weapon
 1988-water disinfectant
 History
 Bromine
 Prior to 1826 Justus von Liebig (German) isolated bromine but he interpreted its
properties (between those of chlorine and iodine) as indicative of iodine chloride
 1826 Antoine Je´rome Balard (French) noted that bromine could be
liberated from a solution of residues remaining after sodium chloride had been
removed from sea water by bubbling chlorine through the solution. He deduced
that this was a new element similar to chlorine because the distillation of these
residues (containing MgBr2 ) with manganese dioxide and sulfuric acid also
produces bromine and is analogous to a known procedure for producing chlorine.
 Iodine
 1811 - Bernard Courtois (French) noted a violet vapor from the ashes of burnt
seaweed and called it ‘substance X’.
 1813- Davy called substance X, iodine.
 Astatine
 First prepared in 1940 by bombardment of bismuth with alpha particles.
 Why Halides
 Many important industrial and medicinal
applications

 Fluoride Chlorine Bromine Iodine

Selected uses of halogens
 Radiopharmaceuticals- positron emission
topography-18F labeled compounds.
 Disinfectants, bleach, and antiseptics -
chlorine 7 iodine compounds.
 Health care-toothpaste, ….
 Photography- Silver bromides
 Industry – fabrics, polymers, ….
Fluorocarbons, Freon (refrigerants) …
 Food- salts
 Synthesis – organic, inorganic, polymers…
 Mineralogy - uranium hexafluoride which is
required for the separation of the isotopes
of uranium in centrifuges.
 Nature but always in compounds
Occurrence
 Fluorine –
 Minerals e.g. CaF2 (Fluorospar), CaF2.3Ca3(PO4)2 (fluorapatite).
 Elemental Florine – electrolysis
2HF + 2KF → 2KF + H2 + F2
 Chlorine
 Minerals e.g. NaCl in large underground salt deposits (formed by evaporation of
ancient seas).
 Sea water
 Elemental chlorine – electrolysis of aqueous NaCl.
 Bromine
 Sea water
 Elemental Bromine – oxidation bromide (Br-) of sea water with Cl2
 Cl2 + 2Br- → 2Cl- + Br2
 Iodine – semi-metal conduct electricity under pressure
 Nature – NaIO3 (sodium iodate)
 Elemental Iodine – oxidation iodide (I-)of sea water with Cl2
 Cl2 + 2I- → 2Cl- + I2
 Reduction of NaIO3
 Astatine - radioactive
 209
83 Bi + α (42He) → 213 85 As
85 As – x 0n → 85 As (x = 1,2 or 3)
 213 1 213-x
 Group 17 Elements (Halogens)
 Pure non-metallic, note I2 semi-metallic at high pressure.

 Halogens are 1e- short of Noble Gas Configuration (NGC).

 Readily form the halide mono-anion X- or a single covalent R-X.

 Elemental halogens are the single-bonded dimmer X-X (not found in nature) are
very reactive toward reduction to halides X- and toward the formation of RX.

 F2 is highly reactive because of the weak F-F bond strength and strong F-substrate
bond strength.

 All halogens except fluorine form compounds with positive oxidation states-
hypervalent compounds involving nd or (n+1)p orbitals in their bonding. e.g. ClF3,
ClF5….

 Iodine compounds in positive oxidation states are stable.

 Elements
 Under normal conditions halogens exist as diatomic, although X4 species
have been detected in the gas phase.
2I2 ↔ I4 (1.4 mol% at 240 C and 2.5 atm)

 The dimmer is held together by van deer Waals attractions rather

than covalent bonds

 The distance between non-bonding I atoms =3.56 Å much

shorted than the van deer Waals radius of iodine
(2x2.15) Å.

 On the application of high pressure solid I2 starts to

develop electrical properties typical behavior of
metals.
 Electronegativity of Fluorine
 Highest electronegative element-ionic character of A-F
bond-pπ -pπ or pπ -dπ bonding
 Account for Lewis acidity of BX3
BF3<BCl3<BBr3
 When react with donor molecule D, pπ -pπ bonding is
destroyed Selected
Electronegativities
(Pauling Scale)

F F
+
F
F 4.0

-
Cl 3.0
B
B F O 3.5
N 3.0
F
F S 2.5
C 2.5
H 2.1
B 2.0
Na 0.9
 Fluorine
 The most EN element-
 Extremely corrosive- the most reactive
element
 Combines directly with all elements
except O2, N2 and lighter Nobel gases
 Chemical Synthesis

K2MnF6 + 2SbF5 → 2KSbF6 + MnF4 @ 150 C

MnF4 → MnF3 + ½ F2
 Electrochemical synthesis of
fluorine

 Electrolysis of a melt of KF and x HF (x ~ 2) @ 70 – 130 °C. The melting points decrease with
the increasing HF concentration: KF x HF 217 °C; KF x 3 HF 66 °C.
 Write a balanced redox equation for the electrolysis of KF in HF and explain why the electrolysis
could not be performed in aqueous media?

 F2 + 2e- → 2F- E0 = +2.87 V

 Cl2 + 2e- → 2Cl- + 2e- E0 = +1.36 V
 Fluorine
 ½ F2(g) → F-(g)

Heat of Formation & Hydration energies of halide ions

Ion ∆ Hf kJ/mol Hydration Energies
½ X2(g) → X- kJ/mol
X-(g) →X-(aq)
F- -259.8 -506
Cl- -233.0 -369
Br- -234.3 -335
I- -226.0 -293
 MO Diagram For F2
σ ∗2pz

π ∗2py π ∗2px

π 2py π 2px
σ *← π *
y
x
z σ 2pz F2 Yellow
Cl2 Green
σ ∗2s
Br2 Red-
brown
σ 2s
I2 purple
 Halogen Solvent interactions
σ ∗2s

π ∗2py π ∗2px π ∗2py π ∗2px

I2 molecule I2-solvent complex Solvent molecule

H3C CH3
I I H3C N I I N
CH3
2.67 Å 2.27 Å 2.83 Å CH3
H3C
< N-I-I = 180 °
 Reactions of Fluorine
 Reacts with hydrogen
F2 (g) + H2 → 2HF (Even in the dark and at low temperature)
 Reacts violently with water
2 F2 + 2 H2O → 4 HF + O2 (may contain O3)
 Reacts with sulfur, selenium, and tellurium, which melt and ignite in the gas,
forming halides.
 Sn + F2 → SF2, SF4, ….
 Powerful oxidizing agent
e.g. F2 + 2KClO3 + H2O → 2HF + KClO4

 Reaction with oxygen or Nitrogen

F2 + X2 → NR (X = O or N)
 Reaction with Cl2
F2 + Cl2 → ClF, ClF3, …
 Reaction with Br2 and I2
F2 + Br2 → BrF3
F2 + I2 → IF5
 Reactions of Fluorine
 Reaction with OH-
2F2 + 2OH- → OF2 + H2O + 2F-
 Properties of OF2
 Stronger oxidizing agent than F2 or O2
 Unreactive unless activated by ED (electric
discharge)
 Has a small dipole moment 0.297 D.
 Lowest boiling point of any inorganic compound,
49 K.
 Other Oxygen Fluorides

F2 + H2O → HOF + HF at -50 °C

HOF + H2O → HF + H2O2

HOF + F2 → HF + OF2

NF3 µ = 0.235 D, bp = 153 K

Cis-FN=FN µ = 0.16 D, bp = 167.5 K

 Poly-tetrafluoroethylene, PTFE (TEFLON) -
Discovery
 April 6, 1938, at DuPont's Jackson Laboratory in New Jersey. DuPont chemist, Dr. Roy J. Plunkett, was working
with gases related to Freon® refrigerants, another DuPont product. Upon checking a frozen, compressed sample of
TFE, he and his associates discovered that the sample had polymerized spontaneously into a white, waxy solid to
form (PTFE).

 The invention of PTFE has been described as "an example of serendipity, a flash of genius, a lucky accident ... even
a mixture of all three." Whatever the exact circumstances of the discovery, one thing is certain: PTFE revolutionized
the plastics industry and, in turn, gave birth to limitless applications of benefit to mankind.

 In 1990, U.S. President George Bush presented the National Medal of Technology to DuPont for the company's
pioneering role in the development and commercialization of man-made polymers over the last half century. The
citation lists Teflon® as one of these special products.

 Dr. Roy Plunkett (1911-1994) has been recognized the world over by scientific, academic and civic communities. He
was inducted into the Plastics Hall of Fame in 1973, and, in 1985, into the National Inventors' Hall of Fame joining
such distinguished scientists and innovators as Thomas Edison, Louis Pasteur and the Wright Brothers.
 Poly-tetrafluoroethylene, PTFE
(TEFLON)
 Synthesis- free radical polymerization

Free radical initiator F

F F e.g. H2O2, HCl, hv...
c F
C
 c
Polymerization techniques such as plasma and catalytic are used for the
F F TFE C
polymerization of
F n
 PTFE - MYSTERY OF A MILLION USESF
 Synthesis of TFE
From Fluorospar

CaF2 +H2SO4 → CaSO4 + 2HF

CH4 +3Cl2 → CHCl3 +3HCl

CHCl3 +2HF → CHClF2 + 2HCl

2CHClF2 → CF2=CF2 + 2HCl

 Catalytic polymerization
 Ziegler-Natta (Nobel 1963)
 Ziegler-Natta Catalyst
 Combination of a transition metal
compound of an element from groups 4
-8 and an organometallic compound of a
metal from groups 1 , 2 or 13.

 Catalyst – Transition metal

 Co-catalyst – Organometallic Compound
 Ziegler-Natta Catalyst
 Most important combination :
 Titanium trichloride + diethylaluminum chloride

Cl Cl

Ti Al
H3C
Cl Cl CH2 CH2

TiCl3 Al(C2H5)2Cl CH3

Or Titanium tetrachloride + triethylaluminum

CH3
Cl H2C

Cl Ti Al
Cl H3C
CH2 CH2
TiCl4 Al(C2H
Cl ) Cl
5 2 CH3
Mechanism of polymerization
Conformation
PTFE
Conformation of polyethylene
(PE)
Comparison of Polymerization Energies in Ethylene and
Tetrafluoroethylene

5 Ethylen Monomers Polyethylene 5 TFE PTFE Polymer (10

Polymer (10 Carbons) Monomers Carbons)

84.01 kcal/mol -59.50 kcal/mol -796.82 kcal/mol -1061.54 kcal/mol

 Properties of TFE
 PTFE has a linear molecular structure of repeating –CF2-CF2-units

 PTFE is a crystalline polymer with a melting point of about 621°F (327°C).

 Density is 2.13 to 2.19 g/cm3.

 PTFE has exceptional resistance to chemicals. Its dielectric constant (2.1) and stable across
wide temperature and frequency range.

 PTFE has useful mechanical properties from cryogenic temperatures at 500°F (280°C)
continuous service temperatures.

 Its coefficient of friction is lower than almost any other material.

 PTFE shows nearly universal chemical resistance (exceptions: elemental fluorine, CF3,
molten alkali metals).

 Impact strength is high, but tensile strength, wear resistance, and creep resistance are low in
comparison to other engineering plastics. glass fiber, bronze, carbon, and graphite sometimes
are added to improve specific mechanical properties.
 Properties of TFE
 PTFE is insoluble in all solvents below 300°C

 High service temperature stability up to 250°C

 Very low adhesiveness

 Very low friction coefficient

 Extremely hydrophobic

 Physiologically inert, i.e. contaminant free

 Very good electrical (high resistance) and dielectrical (very low dielectric number and
loss factor) properties

 Nonflammable

 highly weather resistant (UV resistant)

 Potential Applications
 Optical Materials
 Semiconductors and Processing Materials
 Dielectric Materials
 Release Materials
 Specialized Chemical/Industrial Materials
 Fiber Optics
 Integrated Optics
 Biomedical Materials
 Other Applications

 How many ways can you think of to use Teflon? The potential
applications are limitless—and so are the opportunities.
 Hydrogen Fluoride (HF)
 Weak acid - pKa = 3 (high H-F bond
strength)
 Extremely corrosive, etches glass readily
(see above).
 Even a small spill of dilute HF solution can be
fatal –
 calcium gluconate gel should always be on
hand to treat
 Liquid HF shows very strong hydrogen bonds
unusual Boiling point (HF = + 20 °C vs HCl =
F F
- 84 °C). F F F

H H H
H H
 In-course test
 March 30, 2006 @ 1:00 pm
 Venue : Old Dramatic Theater
 Halogen Hydrides
 HX , stability decreases down the group due to
incompatibility between the hydrogen 1s and the
halogen np orbitals.
 F is the highest electronegative element and hence
for strong bond with H-F-H-F p
 Synthesis
 CaF2 + H2SO4 → CaSO4 + 2HF

 NaCl + H2SO4 → NaHSO4 + HCl @ 150 C

 NaCl + NaHSO4 → Na2SO4 + HCl @ 540-600 C

 2P(red) + 6H2O + X2 → 2H3SO3 + 6HX (X=Br or I)

 Chlorine
 Concentrations as low as 3.5 ppm can be detected by smell
while concentrations of 1000 ppm can be fatal after a few deep
breaths.

 Large amounts of chlorine are used in many industrial

processes, such as in the production of paper products,
plastics, dyes, textiles, solvents and paints.

 The technical synthesis is by electrolysis of aqueous NaCl

Solutions.

 In the laboratory, Cl2 can be made by oxidation of HCl

4HCl + MnO2 → Cl2 + MnCl2 + 2H2O

 16HCl + 2KMnO4 → 5Cl2 + 2MnCl2 + 2KCl + 8H2O

 Reaction of X2 (X = Cl, Br, I) with K
 Redox reaction –violent

 2K + Cl2 → 2 KCl
 Na reacts only with Br2 and not with I2
 Hydrogen Chloride
 Synthesis
 See synthesis of halogen hydrides
 H2(g) + Cl2(g) → 2HCl(g) (explosion)

 Properties

 HCl is very soluble in water, when 1 kg of water is

saturated with HCl at 15 °C, it increases in weight to
1.75 kg, and the relative density is 1.231. It contains
~ 43 % of HCl; commercial HCl conc. contains ~ 39
%.
 A concentrated solution of HCl is strongly acidic but
not oxidizing. It can dissolve Zn, Al, Fe but not Cu, Hg,
Ag, Au and Pt.
 Acid-base reactions

 NH4Cl + H2SO4 → NH4HSO4 + HCl(g)

 NH4Cl + NaOH → NaCl + H2O + NH3(g)
 NH3(g) + HCl(g) → NH4Cl(s)
 Chlorine oxides
 Dichlorine oxide -Cl2O-
 Synthesis –
2 HOCl ↔ Cl2O + H2O

i.e. Cl2O is the anhydride of hypochlorous acid, HOCl.

 Properties - A yellow-red gas, which can explode
into the elements O2 and Cl2 upon heating.

Cl2O → Cl2 + ½ O2
O
Cl Cl
<Cl-O-Cl = 111 °
d(Cl-O) = 1.70 Å
 Oxides of Chlorine
 Chlorine dioxide –ClO2 Cl
A yellow gas, very explosive.
Synthesis: (see chlorous acid) O O
5HClO2 → 4ClO2 + HCl + H2O
<O-Cl-O = 118 °
d(O-Cl) = 1.40 Å

 Dichlorine heptoxide - Cl2O7- is the most stable oxide of

chlorine. It is the anhydride of perchloric acid, HClO4.
O O
O O

Cl Cl

O
O O

<O-Cl-O = 118 °
d(O-Cl) = 1.70 Å
D(Cl=O) = 1.41 Å

 Other, less important oxides: Cl2O3, Cl2O4, Cl2O6.

 Oxoacids of chlorine
Compound HOCl HOClO HOClO2 HOClO3
Oxidation state+1 +3 +5 +7

pKa 7.4 2 -2.7 -8

Anion name Hypochlorit Chlorite Chlorate perchlorate
e
Uses Bleach Matches, explosives
O O
OH
fireworks
Cl O X X Cl
O O O O
H HO
HO

Hypochlorous acid Halous acid Halic acid Perchloric acid

O O O
X-
X-
-Cl O X- O
O O O
HO O
Hypohalite Halite Halite Perhalate
 Oxoacids of chlorine
 All are good oxidizing agents.
 The acid strength and the stability increases
with the oxidation state.
 Only HClO4 can be isolated in pure form (all
others as aqueous solutions).
 Hypochlorous Acid (HOCl)
 Synthesis – disproportionation* of Cl2 in H2O.
Cl2 + H2O HOCl + HCl

 HOCl is a weak acid

 & a strong oxidizing agent
Bleaching with hypochlorite.

 Salts of hypochlorites
Cl2 + 2 NaOH → NaOCl + NaCl + H2O
Cl2 + Ca(OH)2 → CaCl(OCl) + H2O
 Usage of Hypochlorites
 Bleaching
 Disinfect swimming pool

*Disproportionation: oxidation-reduction reaction in which the same element is both oxidized and
reduced.
 Chlorous Acid (HClO2)
 Synthesis – reaction of chlorite with acid

e.g. Ba(ClO2)2 + H2SO4 → 2 HClO2 + BaSO4

 Properties – unstable –disproportionate

5 HClO2 → 4 ClO2 + HCl + H2O

O.S.(Cl) 3+ 4+ -1
 Chloric Acid (HClO3)
 Synthesis – reaction of chlorate with acid

e.g. Ba(ClO3)2 + H2SO4 → 2 HClO3 + BaSO4

 Chlorates salts –synthesis

 disproportionation of hypochlorites upon heating.
The anion is oxidized by the free acid
2 HClO + ClO- → ClO3- + 2 HCl
OS(Cl) +1 +1 +5 -1
 Reaction of Cl2 with hot bases
3 Cl2 + 6 OH- → ClO3- + 5 Cl- + 3H2O
OS(Cl) 0 +5 -1
 Reaction of chlorates with
oxidizable species
 Chlorate are strong oxidizing species
and explode when mixed with
oxidizable substances such as sugar,
phosphorus, sulphure…
e.g. 5KClO3 + 6 P → 5 KCl + 1.5 P4O10
 Reaction of chlorates with
sugar
H2SO4
 8 KClO3 + C12H12O11 → 8 KCl + CO2 + 11H2O

 KClO3 is a weak oxidizing agent, the addition of

H2SO4 makes HClO3 a very strong oxidizing
agent
 Perchloric acid – HClO4
 Synthesis
 RXN perchlorate with acid→
NaClO4 + HCl → NaCl + HClO4
 Anodic oxidation of chlorate
ClO3- + H2O ↔ ClO4- + 2H+ + 2e-
 Disproportionation of chlorate

4 KClO3 → 3 KClO4 + KCl

 Properties
 HClO4 is a colorless liquid (mp. – 101 °C, bp. 120 °C)
which can decompose with an explosion upon heating.
 Aqueous solutions are stable and very strong acids.
 The perchlorate anion
 Lewis structure
 Bromine
 First reported in 1828 and named after the Greek word for stench, bromos.
 The only nonmetallic element that is a liquid at room temperature (mp = - 7 °C).
 Bromine will quickly eat its way through rubber and plastic bottle tops and even
attacks teflon.
 Elemental bromine is a hazardous material. It causes severe burns when it
comes in contact with the skin and its vapor irritates the eyes, nose and throat.
 Much of the bromine output was used in the production of ethylene dibromide
(C2H4Br2), a lead (Pb) scavenger used in making gasoline anti-knock compounds.
 Synthesis
 Oxidation of bromide
 With Cl2.
2KBr + Cl2 → 2KCl + Br2
2e- + Cl2 ↔ 2Cl- E0 = 1.358 V
2Br- ↔ 2e- + Br2 E0 = 1.065 V
 With MnO2
2KBr + H2SO4 → 2HCl + K2SO4
4 HBr + MnO2 → MnBr2 + 2H2O + Br2
 Reaction of Bromine with red
phosphorous
< 84 C

 P + Br2(l) → PBr3(g) + Br2(g) ↔ [PBr4]Br-

> 84 C
 Reaction of Bromine with non-metals
 2Al + 3 Br2(l) → 2AlBr3(g)
 Br2 is less reactive than Cl2, however in its highly
concentrated liquid form it binds to other
elements (e.g. As, Sb, Sn) and undergoes violent
redox reactions.
 Hydrogen
Bromide
 Synthesis
 Reaction of bromides with sulfuric acid
because of partial oxidation to bromine:
2KBr + H2SO4 → K2SO4 + 2 HBr
2HBr + H2SO4 → 2 H2O + SO2 + Br2
 Diluted or non-oxidizing acid such as H3PO4.
3KBr + H3PO4 → K3PO4 + 3 HBr
 Note: HBr is a stronger reducing agent than
HCl.
2HBr + Cl2 → Br2 + 2HCl
 Hypobromous Acid
(HOBr)
 Synthesis
 Reaction of bromides water with mercury oxide :
2Br2 + 3HgO + H2O → HgBr2.2HgO + 2 HOBr
Note: HOBr is a weaker acid than HOCl
 Hypobromites (salts of HOBr)
 Synthesis : reaction of bromine with NaOH at 0°
2Br2 + 2NaOH → NaBr+ NaOBr + H2O
 Above 0° hypobromites disproportionate into
bromide and bromate:
3BrO- → 2Br- + BrO3-
 Iodine
 Iodine was discovered by the French chemist
Barnard Courtois in 1811.

 Today, iodine is obtained from deposits of

sodium iodate (NaIO3) and sodium periodate
(NaIO4) in Chile and Bolivia.

 Iodine is a bluish-black solid, volatizing at

ambient temperatures into a blue-violet gas with
an irritating odor.

 Thirty isotopes are recognized. Only one stable

isotope, 127I is found in nature.

 Trace amounts of iodine are required by the

human body (Iodine is part of the hormone
thyroxin). A lack of iodine can also cause a
goiter, a swelling of the thyroid gland. Iodine is
added to salt (iodized salt) to prevent these
diseases.
 Synthesis
 Oxidation of iodides with Cl2.
2KI + Cl2 → 2 KCl + I2

Cl2 + 2e- ↔ 2Cl- E0 = 1.36 V

2I- ↔ I2 + 2e- E0 = 0.54 V

 Oxidation of hydrogen iodide

2KI + H2SO4 → 2 HI + K2SO4

4KI + MnO2 → MnI2 + 2H2O + I2
 Charge-transfer complexes
 Solutions of iodine (electron acceptor)
and heteroatoms-containing solvents
(electron donor) are highly colored due
to partial charge transfer from donor
to acceptor.
I2 + :D → I2δ-….. δ+:D
 Iodine-starch interaction
 Natural starches are mixtures of amylose (10-20%) and
amylopectin (80-90%).
 Iodine is not very soluble in water, but it dissolves in the
presence of potassium iodide. The resulting I3- ion slips into
the coil of the starch causing an intense blue-black color.
 Interhalogens
 Halogens react with each other to form a
wide variety of interhalogen compounds are
known (see below)
Neutral
XF XF3 XF5 X = Cl, Br or
I
BrCl (ICl3)2 IF6, IF7

Cationic
ClFCl+ XF4- XF6+
ClF2+

Anionic
BrCl2- ClF4- BrF6-
ICl2- BrF4- IF6-
 Synthesis of Interhalogens
 Neutral

 Direct mixing of different halogens under different conditions that

vary with the nature of halogen -
Y2(g) + 3 F2(g) → 2YF3(g) (Y = Cl, T = 200-300; Y = Br, T = 20; Y = I, T = -45 in CFCl3
solvent)
I2(g) + 3 Cl2(g) → I2Cl6(g) (T = -80 C, readily dissociate to ICl & Cl2)
Y2(g) + 5 F2(g) → 2YF5(g) (Y = Cl, T = 350, p =250 atm; Y = Br, T > 150; Y = I, T = 20)
 Organosubstitution
C2F5I(g) + ClF3(g) (or BrF5) → C2F5IF4
CH3I(g) + XeF2(g) → CH3IF2
C2H5I(g) + Cl2(g) → C6H5ICl2 (in CHCl3)
 Disproportionation
5IF → 2I2 + IF5
 Interhalogens

 For diatomic
½ X2(g) + ½ Y2(g) → XY(g) (25C, 1atm ∆ S = 4.6-5.4 JK ) -1

 Stability due to ∆ Hf
IF>BrF>ClF>ICl>IBr>BrCl
 ~ electronegativity differences of elements due to electrostatic
contribution to the bonding arising from charge separation Yδ +-Xδ -
 Bond length ~ ∑covalent radii when electronegativity difference
between the two halogens is small.
 Although ∆ Hf of IF shows that it is the most stable, it is unstable to
disproportionation
5IF → 2I2 + IF5
 Structure of interhalogens
 Use VSEPR to predict shape of
interhalogens
 Organometallics of Main Group
Elements

 References - Web-based

 http://www.cem.msu.edu/~reusch/Vir
 Organometallics of Main Group
Elements
What is an organometallic? An
organometallic molecule is one that
contains a bonding interaction (ionic or
covalent, localized or delocalized) between a
metal-carbon bond.
Note :
 metal – main group or transition metal
 More than one M-C bond maybe present
 The term organometallic is usually rather loosely defined
and organic derivatives of the metalloids (boron, silicon,
germanium, arsenic, and tellurium) will be included in this
definition.
 Why Organometallics?
 Play an major role in Organic and Materials
chemistries - alkylating or arylating agents

 Organometallics also play smaller but important

roles in other branches of chemistry such as
Biological and Analytical.

 Catalysts for many organic transformations.

 First Organometallics*,**
 An Alkyl Zinc Reagent 1849 E. Frankland
R-X + Zn → Rδ --Znδ +-Xδ -
 A Grignard Reagent 1900 V. Grignard
R-X + Mg → Rδ --Mgδ +-Xδ -
 An Alkyl Lithium Reagent 1930 K. Ziegler
R-X + 2Li → Rδ --Liδ + + LiX

*Prepared from reductive substitution of alkyl halides

**All metals have strong or moderate negative
potential
 Classification
Molecular
electron-poor

1 2 12 13 14 15
Li Be B
Na Mg Al Si
K Ca Zn Ga Ge As
Rb Sr Cd In Sn Sb
Cs Ba Hg Tl Pb Bi
Hypoelectronic
Red ionic Covalent divide Molecular
Yellow polymeric molecular electron-rich
Blue Covalent electron-precise
Hyperelectronic
 Reactivity
Increase

1 2 12 13 14 15
Li Be B
Na Mg Al Si
K Ca Zn Ga Ge As
Rb Sr Cd In Sn Sb
Cs Ba Hg Tl Pb Bi

In general, the reactivity parallels the ionic character of the

carbon-metal bond
% Ionic Character of H3C – Metal (CH3)2Hg < (CH3)2Cd < (CH3)2Zn < (CH3)2Mg < CH3Li
 Road-map

 Synthesis
 Structure and bonding
 Reactivity
 Utility or uses if applicable?
 General Synthetic Methods
1
 Direct Reactions of Metals with
alkylhalides (see first organometallics)
 Reduction of alkylhalides with
electropositive elements

e.g. Mg + CH3I → CH3MgI

Direct interactions of alkyl and aryl halides occur

with Li, Na, K, Mg, Ca, Zn and Cd.
 General Synthetic Methods
2
 Use of Alkylating Agents – important
alkylating agents – Grignard and lithium,
aluminum, Hg and sodium derivatives
especially Na+C5H5-.

e.g. PCl3 + 3C6H5MgCl → P(C6H5)3 + 3MgCl2

 Most nonmetal and metal halides or halide

derivatives can be alkylated in ether or
hydrocarbon solvent
 General Synthetic Methods
3
 Interaction of Metal and Nonmetal
Hydrides with Alkenes or Alkynes
ether
e.g. ½ B2H6 + 3R2C=CR2 → B(R2C-CR3)3
B(R2C-CR3)3+ H2O2 → B(OH)3 + R2(OH)C-CR3
 General Synthetic Methods
4
 Insertion Reaction

e.g. SbCl5 + 2HC≡CH → SbCl3(HC=CHCl)2

 Alkali Metals
Organometallics
 Lithium Alkyls and Aryls
 Synthesis
 Direct reaction of metal with alkyl halide
2Li + RX → LiX + [LiR]

R = alkyl or aryl and X = halide

 Metal-metal exchange

2Li + HgR2 → 2LiR +Hg Dry N2, hydrocarbon solvent

 Alkali Metals
Organometallics
 Lithium Alkyls and Aryls
 Synthesis
 Metal-hydrogen exchange

Li
LiC4H9 + Fe → Fe + C4H10
 Alkali Metals Organometallics
 Lithium Alkyls and Aryls
 Synthesis
 Metal-halogen exchange

Br Li

LiC4H9 + → + C4H10
N N
 Alkali Metals Organometallics
 Lithium Alkyls and Aryls
 Properties
 Organolithium -Spontaneously flammable in air or water due to oxidation
and hydrolysis.

 Organolithium bromides or iodides – form stable solid complexes of

stoichiometry RLi(LiX)1-6

 Soluble in non-polar solvents – covalent nature

 High volatility – covalent nature

 In general liquids or low melting solids – covalent nature

 Lithium alkyls
 Bonding

 Electron-deficient 2e- multiceter type bond.

 Aggregate formation is due to Li-C-Li bonding rather than Li-Li bonding interaction.
Li CH3
H3 C Li

H3 C Li
Li CH3
-43 kcal/mol Li CH3
-85 kcal/mol

CH3 Li

Li CH3

H3 C Li
-131 kcal/mol
Li CH3

-119 kcal/mol

Alkali Metals Organometallics
Lithium Alkyls and Aryls
 Structure
 Molecular association is an important feature in both crystals and solutions- (CH3Li)n (n = 1, 2, 3, 4, 6…)
 Solid State - MeLi – tetramer- (CH3Li)4 and others were determined

 Li is in the corners of a tetrahedron with alkyl groups centered over the facial planes with CH3 group
symmetrically bound to three Li atoms, the alkyl bridged bonding is of the electron-deficient multi-ceter type
(2e--4centered bond).
 Aggregate formation is due to Li-C-Li bonding rather than Li-Li bonding interaction.
 Lithium alkyls
 Bonding

 Electron-deficient multi-ceter type (2e--4centered bond).

 Aggregate formation is due to Li-C-Li bonding rather than Li-Li bonding interaction.

3Li+ :CH3-

 3Li 1s22s12p0 → sp3, Li+ 1s22s02p0 → sp3

 6
C 1s22s22p2 → sp3, C- 1s22s22p3 → sp3 (3Li-CH3)2+
 Alkali Metals Organometallics
 Lithium Alkyls and Aryls
 Solution – structure depends on

 Solvent - polar or non-polar

 Temperature

 Steric nature of the organic radical

 Concentration

 In hydrocarbons –MeLi, EtLi, Pr-Li and others are hexamers and tert-butylLi is
tetramer But- bulky.

 In ether and amines tetramers are formed.

O
 BenzylLi is monomer in THF –tetrahydrofuran

 Monomers react faster than aggregates. THF

 Alkali Metals
Organometallics
 Reactions of organolithium - carbanionic in nature- [R3C:]-

 Halide abstraction – nucleophilic substitution reactions

e.g. Liδ +- δ Bu + CH2=Cδ +- δ Br(H) → LiBr + CH2=CHBu dry N2

 LiR + RI → R-R + LiI (C-C coupling)
 LiR + BCl → BR + 3LiCl
3 3
 LiR + HgBr → HgR + 2LiBr R:- R δ + - -δ X
2 2
 LiR + SnCl → Cl SnR + xLiCl
4 4-x x

 Proton abstraction- acid-base reaction

e.g. Liδ +- δ
Bu + C6F5H → BuH + C6F5Li dry N2
LiR + HX → RH + LiX dry N2
 Some Reactions of
LiR
 Reaction with halogens
LiR + X2 → RX + LiX (Reduction)
 Addition Reactions
e.g. BR3 + LiR→ Li+BR4-

 Reactions with ketones & CO2

 LiR + Ar2C=O +H2O → Ar2C(R)OH + LiOH
Propose a mechanism?
 LiR + CO2 +H2O → RCOOH + LiOH
 Thermal decomposition
 LiR → olefin + LiH heat
 Organosodium and organopotassium
compounds

 Synthesis –prepared in situ as highly reactive intermediates

2M + HgR2 → 2MR +Hg Dry N2, hydrocarbon solvent

2M + RX → MX + [MR]
[MR] + RX → MX + R-R (Wurtz coupling)
Important reactions:
3 C5H6 + 2Na → 2C5H5-Na+ + C5H8
C5H5- =
RC≡Cδ - +δ+δ H + Na → RC ≡C-Na+ + ½ H2

Solvent used : THF , DMF (dimethyl formamide) cyclopentadiene anion (Cp)

H
 Properties H
H
H
O
 Ionic – monomers N H
H
 Insoluble in hydrocarbons THF O

 Highly reactive, sensitive to air and water. H

DMF
 Alkaline Earth Metals Organometallics
 The alkaline earth metals

H
Li Be B
Na Mg Al
K Ca Ga
Rb Sr In
Victor Grignard
Cs Ba Tl
Nobel 1912
 In 1898, while a student under Philippe Barbier at Lyon, Grignard began his prizewinning work
with a study of the alkylzinc compounds developed earlier by Sir Edward Frankland. It was Barbier
who had Grignard repeat some experiments on the preparation of a tertiary alcohol from a
mixture of methyl heptyl ketone, magnesium, and methyl iodide. Grignard hit upon the idea of
treating the iodide with the magnesium first and carried out the reaction in ether. This first of the
Grignard reagents was a complete success. Grignard's doctoral dissertation (1901) described the
preparation of alcohols, acids, and hydrocarbons by means of reactions of organomagnesium
compounds. He became professor of chemistry at Nancy (1910) and at Lyon (1919). At the time of
his death some 6,000 papers reporting applications of the Grignard reaction had been published
 Alkaline Earth Metals Organometallics
 Mg + RX → RMgX (Grignard Reagent)
 Intermediates –solvation
H3C O
C 2H 5
OEt2 Br OH8C4 Mg
Br O
Mg Mg OC4H8
(CH3CH2)2O O
OEt2 C2H5 OH8C4
Br

Td TBP diethyl ether

OC4H8 =THF
 Polymeric at conc. > 0.3 M-diethyl ether solution
OEt2 X X Br OPri
Br H5C2
Mg Mg Mg Mg Mg
OEt2 R OEt2 OPri C 2 H5
C6H5 OEt R Br
2

 (Bridging properties Cl>Br>I)

 In strongly coordinating solvents such as Et3N & THF Grignard reagents (GR) are
monomers.
 Disproportionation
 2RMgX ↔ MgR2 + MgX2
 In ether insignificant but in a solvent that may complex with one intermediate than the
others the equilibrium may shift to the left.
 Grignard Reagent
 Intermediates – solution equilibrium

X R X
X X
R Mg Mg Mg
Mg Mg
Mg R R X
R R
X

R
X
Mg
R Mg
X
 e.g. In dioxane- MgX2.2C4H8O2 is formed.
2RMgX + 2C4H8O2→ R2Mg +
MgX2.2C4H8O2↓
O

1,4-dioxane
 Some Reactions of Alkaline Earth Metals
Organometallics
 Reaction with acid

RMgX + HX → RH MgX2

 Reaction with halogen

RMgX + X2 → RX + MgX2

 Reactions with halides

 RMgX + BCl3 → BR3

 RMgX + SnCl4 → SnR4
 Some Reactions of Alkaline Earth Metals
Organometallics
 Reactions with ketones & CO2

 RMgX + H2C=O +H2O → RCH2OH

 RMgX + R’HC=O +H2O → RR’CHOH
 RMgX + R’2C=O +H2O → R’2RCOH
 RMgX + CO2 + H+ → RCOOH

 Synthesis of other Organometallics

 BeCl2 + 2RMgX → BeR2 + 2MgXCl

R = Methyl-polymeric white solid
 Structure of Be(CH3)2
 Polymeric – 2e--3c bonding

H 3C CH3 CH3
H3C CH3
H 3C
Be Be Be Be
Be
H 3C CH3 CH3 CH3
CH3
CH3

 Show the bonding in Be(CH3)2

 4Be 1s22s2p0 → sp3
 6
C 1s22s2p2 → sp3
 When R = Methyl –polymeric-3 centered-2 e’s-sp3 Be-1-e
from Me CH3
HC3 CH3 CH3
Be Be Be
H 3C CH3 CH3 CH3

 For other alkyl groups dimeric, unless steric interactions –

monomeric. e.g. di-tert-butyl beryllium

H3C CH3

C Be C CH3
H3C
CH3 CH3

 linear at RT
 For Ca, Sr and Ba-organometallics are very reactive
 Large size
 Low solubility compared to Mg compounds
 M-C bond is more ionic
 Metal center coordinatively unsaturated
Mg
 Polymerization
 e.g. Mg(C5H5)2 sandwich-like structure
 Ca(C5H5)2 polymeric insoluble solid.
 Pyrolysis of alkyl beryllium

 (CH3)3CMgBr + BeCl2 → [(CH3)3C]2Be

↓Heat
2(CH3)2C=CH2 + BeH2

 BeH2 + B2H6 → Be(BH4)2

H H
H H
 B-H-Be & B-H-Be B Be B

 3c/2e- bonds H
H H
H
 Synthesis of Ca, Sr and Ba
Organometalics
 Transmetallation ( metal exchange)
2RM’ + MX2 → RMX + 2M’ X (in ether)
2RM’ + MX2 → R2M(THF)2 (in THF)
M’ = Li, Na, K; M = Ca, Sr, Ba
 Metal vapor deposition
Ca + RX → RCaX (solvent free)
R = alkyl or aryl; X = F, Cl or Br)
 Organometallics of Group 13
 MR3
 3CH3MgI + BF3 → (CH3)3B
 3C6H5Li + GaCl3 → (C6H5)3Ga
 4CH3Li + AlCl3 → LiAl(CH3)4
 3C6H5Li + BF3 → (C6H5)3B + C6H5Li → LiB(C6H5)4
 Al + (AlEt3)2 + 3/2 H2 → (AlEt2H)3 + 3C2H4 → 3/2
(AlEt3)2
 AlR3
For Met or Phenyl

Al-C-Al = 77

< Al-C-Al = 75 H3C CH3 CH3 H5C6 C C6H5

<C-Al-C = 105
Al = sp3 Al Al Al Al
Al-C-Al 3c/2e- H3C H 5C 6
CH3 CH3 C C 6H 5

CH3

H3C CH3

Al Al
H 3C CH3

CH3
 Organo Derivatives of Group 14
 MR4
SiCl4 + 4LiR → SiR4
2PbCl2 + 4RMgX → [2PbR2] → Pb + PbR4
 Mixed RnMX4-n
GeCl4 + nLiR → RnGeR4-n
GeBr4 + GeR4 → 2R2GeBr2
GeBr4 + 3 GeR4 → 4R3GeBr

 Si + CH3Cl → CH3SiCH3 + (CH3)2SiCl2 + (CH3)3SiCl

 GeI2 + (Me3Al)2 → [Me3Ge(GeMe2)nGeMe3
 SnCl2 + C6H5MgBr → [Sn(C6H5)2]6

 Lewis acidity
 MX4>RMX3>R2MX2>R3MX
 F>Cl>Br>I
 Sn>Ge>Si
Organo Derivatives of Group 15 Elements
 Trialkyl amines-with unbulky groups adopt pyramidal geometry with the lone pair in the forth
position, with bulky groups such as phenyl or tri-isopropyl planar geometry was observed to
relieve the steric congestion. In contrast the longer P-C bonds in in PPh3 allows the phosphine to
sdopt the normal tetrahedral geometry.

 Synthesis
 Direct reactions of halides with Grignard reagents of Li
 MCl3 + 3RMgX → MR3
 OPCl3 + 3LiR → OPR3
 MCl3 + Cl2 → R3MCl2 + LiR → MR5 + LiR → Li+[MR6]-
 In the presence of limited (deficiency) in Grignard or Li organometallic agents intermediate
organohalides are formed:
 PCl3 + LiR → RPCl2
 PCl3 + 2LiR → R2PCl + Na → R2P-PR2
 Direct Reaction of elements with alkyl halides
 CF3I +P → P(CF3)3 + IP(CF3)2 + I2PCF3

 Organo Derivatives of Group 16
 MR2 derivatives are known (M all except Po)
MX2 + 2LiR → MR2 + 2LiX (M = S, Se or Te, X =Cl)

: C2H5 : C 2H 5
BF3
+ O O
: F 3B C 2H 5
Structure (Td) C2H5

RI + S → SR2 + RS-SR + RS-SSR (Sealed tube)

 R2Se +X2 → R2SeX2 + HgR2→ R3SeX
 R2M + RX → R3MX
 TeMe4 + XeF2 → cis-F2TeMe4 + ZnMe4 → TeMe6
 π -Bonding in Boron Trihalides
 All boron trihalides are monomeric with π −π interactions
between boron and halide.
 Strength of π -π interactions BF3>BCl3>BBr3>BI3.
 B-X-B is not possible because of the small size of B (0.88A)-
leads to steric congestion.
 In Be-Cl-Be possible-Be radius (1.06 Å).
 In [BF4]- d(B-F) = 1.43 Å and in BF3 d(B-F) = 1.30 Å
X X

X X
B X + L B L
B X

X X X

planar Terahedral (Td)

 The small size of B prevents the formation of B3+ cation-due to
the high polarizing power of tiny ion.
 Boron compounds in general are covalent hybridized to either sp2
or sp3 configuration.
 pπ -pπ Bonds
 Only nitrogen forms stable N-N multiple compounds-the rest are metastable.

t-Bu t-Bu
t-Bu
THF
Cl
t-Bu P
t-Bu P + Mg
P t-Bu
Cl

t-Bu
t-Bu t-Bu

 CH3PCl2 – HCl → CH2=PCl –HCl → HC≡ P

HCP Unstable, decompose >10 C, Dipole moment =0.39D C(SiMe3)3
P
 CF3PCl2 – HF → CF 2=PCl –HF →NaFC≡ P
Cl
C(SiMe
3 3) P
Cl
+ P
(SiMe3)3C
 dπ -pπ Bonding
 E.g. O=PR3

π ∗ MO

3dxy 2pz
3d
2px P atom
3dyz 2p

z O atom
x
y
π MO
 Complexes of MR3
 Trivalent derivatives of MR3 behave
either as Lewis acids or bases in
coordination chemistry
 e.g. [Cu(NH3)4]SO4; [Co(NH3)6]Cl3 – 2e-
donor- NH3 ammine
 P & As have d-orbitals that allow d-d-
inteaction with TM.
 With bulky ligands of the type
M(SiMe3)3 (M= P, As or Sb) are able to
act as Lewis bases.
 Hydrides of Boron
 Diborane, B2H6
 Preparation
BF3 + LiAlH4 → B2H6 (ether)
 Bonding
12e-/8 Bonds; ∴ e-deficient molecule; B is sp3 hybrid-
form normal 2e/2c bond with teminal hydrogens using
8e-, this leaves 4e- for the formation of 2e/3c B-H-B
bonds using 1e- from H and 1 e from boron for each
bond. H

H H H H
B B B B
H H H H

AO interaction 3c/2e- MO
 pπ -pπ Bonds
 Only nitrogen forms stable pπ -pπ interactions.
Bond Energies (kJ/mol)
N P
M-M 160 200
M=M 419 310
M≡ M 945 490
*Elemental nitrogen exist as N≡ N.
** P forms a series of singly bonded allotropes.
*** P4 → 2P2 heat >1700 C, d(p-p) = 1.89 Å triple bond; for single P-
P bond d = 2.20 Å.