Chapter 4 -

Introduction to
Transition Metals
I. Introduction to Transition Metal Complexes.
Classical complexes (Jorgenson and Werner)
Survey of ligand coordination numbers, geometries and types of ligands
Nomenclature
Isomerism
II. Bonding in Transition Metal Complexes.
Electron configuration of transition metals
Crystal field theory
Valence bond theory
Simple Molecular Orbital Theory
Electronic Spectra and Magnetism
III. Kinetics and Mechanisms of Inorganic Reactions.
Stability and lability
Substitution reactions
Electron transfer reactions
IV. Descriptive Chemistry of TMs.
V. Organometallic Chemistry
18 e- rule, , and  bonding ligands (synergistic bonding)
Metal carbonyls, synthesis, structure, reactions
Compounds with delocalized -conjugated organic ligands.
Reactions and catalysis
 Transition Metals and
Coordination Chemistry
4.1 The Transition Metals: A Survey
4.2 The First-Row Transition Metals
4.3 Coordination Compounds
4.4 Isomerism
4.5 Bonding in Complex Ions: The Localized Electron
Model
4.6 The Crystal Field Model
4.7 The Biologic Importance of Coordination Complexes
4.8 Metallurgy and Iron and Steel Production
 Transition Metals

• Show great similarities within a given

period as well as within a given vertical
group.
 The Position of the Transition
Elements on the Periodic Table
Plots of the First (Red Dots) and Third (Blue
Dots) Ionization Energies for the First-Row
Transition Metals
Atomic Radii of the 3d, 4d,
and 5d Transition Series
 Forming Ionic Compounds
• Transition metals generally exhibit more than one oxidation
state.

• Cations are often complex ions – species where the transition

metal ion is surrounded by a certain number of ligands (Lewis
bases).

• Most compounds are coloured because the transition metal ion

in the complex ion can absorb visible light of specific
wavelengths.

• Many compounds are paramagnetic.

The Complex Ion Co(NH3)63+
 Electron Configurations

• Example
▪ V: [Ar]4s23d3
▪ Fe: [Ar]4s23d6

• Exceptions: Cr and Cu
▪ Cr: [Ar]4s13d5
▪ Cu: [Ar]4s13d10
 Electron Configurations

• First-row transition metal ions do not have 4s electrons.

▪ Energy of the 3d orbitals is less than that of the 4s orbital.

Ti: [Ar]4s23d2
Ti3+: [Ar]3d1

What is the expected electron configuration of Sc+?

Explain.

[Ar]3d2
3d Transition Metals
• Scandium – chemistry strongly resembles lanthanides
• Titanium – excellent structural material (light weight)
• Vanadium – mostly in alloys with other metals
• Chromium – important industrial material
• Manganese – production of hard steel
• Iron – most abundant heavy metal
• Cobalt – alloys with other metals
• Nickel – plating more active metals; alloys
• Copper – plumbing and electrical applications
• Zinc – galvanizing steel
Oxidation States and Species for
Vanadium in Aqueous Solution
Typical Chromium Compounds
Some Compounds of Manganese in Its
Most Common Oxidation States
Typical Compounds of Iron
Typical Compounds of Cobalt
Typical Compounds of Nickel
Typical Compounds of Copper
Alloys Containing Copper
 A Coordination Compound

• Typically consists of a complex ion

and counterions (anions or cations
as needed to produce a neutral
compound):

[Co(NH3)5Cl]Cl2
[Fe(en)2(NO2)2]2SO4
K3Fe(CN)6
D block chemistry is vast, often thought of in terms of
lewis Acids/Base interactions

Metals act as Lewis acids, which react with Lewis bases.

The Lewis acid/base product is generally called a

coordination complex and the Lewis bases are called
ligands.

Wide variety of d-block chemistry to be addressed։

• geometries։ coordination number (CN = the number of Lewis bases
bonded to the metal) can vary from 2 to 8; 4 and 6 are most common
• Oxidation states։ from negative to +7 or +8
• Bonding nearly purely ionic to nearly purely covalent ; intermediate
much more common
• reactivity։ substitution, addition, elimination, redox – and a number of
mechanisms
 Structures of Coordination
CN = 2, 3
Complexes
Rare, follow VSEPR rules CN = 2 linear [Ag(NH3)2]+; CN = 3,
trigonal planar

CN = 4
Quite common; found in two geometries-tetrahedral (Td) and
square planar (D4h) some complexes are known that are
between Td and D4h (D2d)
Square planar complexes can exhibit geometric isomerism։
ML2L’2 cis or trans makes a difference in the chemistry։ cis-
Pt(NH3)2 Cl2 is an anticancer drug, the trans isomer is inert

CN = 5
Not rare, not common; two geometries-trigonal bipyramid
(D3h) and square-based pyramid (C4V); the two geometries are
generally close in energy so ligands can scramble.
 Berry pseudorotation is seen in mixed ligand complexes, this
scrambles ligand positions։

CN = 6
Most common coordination number, octahedral.
Often an get distortions from Oh
Extension or compression along one axis։ tetragonal։ D4h
Change along two axes։ rhombic։ D2h
Change along the diagonal (the C3 axis)։ D3d
disubstituted ML4L’4։ cis (C2v) or trans (D4h)
trisubstituted ML3L’3։ fac (C3V) or mer (C2v)
 The formation of a coordinate complex is a
Lewis acid-base reaction

Lewis base: NH3 Coordination complex:

Lewis base coordinated
to a Lewis acid

Coordination complex:
Ligand (electron donor)
coordinated to a metal
Lewis acid: Co3+ (electron acceptor)

The number of ligand bonds to the central metal atom is

termed the coordination number
 Coordination Number

• Number of bonds formed between the

metal ion and the ligands in the complex
ion.

▪ 6 and 4 (most common)

▪ 2 and 8 (least common)

 Ligands

• Neutral molecule or ion having a lone electron pair

that can be used to form a bond to a metal ion.

▪ Monodentate ligand – one bond to a metal ion

▪ Bidentate ligand (chelate) – two bonds to a

metal ion

▪ Polydentate ligand – more than two bonds to a

metal ion
 Coordinate Covalent Bond

Bond resulting from the interaction

between a Lewis base (the ligand) and a
Lewis acid (the metal ion).
The Bidentate Ligand
Ethylenediamine and
the Monodentate
Ligand Ammonia
The Coordination of
EDTA with a 2+ Metal
Ion, it is a hexadentate
ligand. Ligands that bind
to more than one site are
called chelating agents.

ethylenediaminetetraacetate
Multidentate ligands
Multidentate ligands
 Rules for Naming Coordination
Compounds
[Co(NH3)5Cl]Cl2

1. Cation is named before the anion.

“chloride” goes last (the counterion)

2. Ligands are named before the metal ion.

ammonia (ammine) and chlorine
(chloro) named before cobalt
 Rules for Naming Coordination
Compounds

[Co(NH3)5Cl]Cl2

3. For negatively charged ligands, an “o” is

added to the root name of an anion
(such as fluoro, bromo, chloro, etc.).

4. The prefixes mono-, di-, tri-, etc., are

used to denote the number of simple
ligands.
penta ammine
 Rules for Naming Coordination
Compounds

[Co(NH3)5Cl]Cl2

5. The oxidation state of the central

metal ion is designated by a Roman
numeral:
cobalt (III)
6. When more than one type of ligand is
present, they are named alphabetically:
pentaamminechloro
 Rules for Naming Coordination
Compounds

[Co(NH3)5Cl]Cl2

7. If the complex ion has a negative

charge, the suffix “ate” is added to the
name of the metal.

The correct name is:

pentaamminechlorocobalt(III) chloride
Name of Metals in Anionic
Complexes
Sample Problem 23.3 Writing Names and Formulas of
Coordination Compounds
PROBLEM:
(a) What is the systematic name of Na3[AlF6]?
(b) What is the sytematic name of [Co(en)2Cl2]NO3?
(c) What is the formula of tetraamminebromochloroplatinum(IV) chloride?
(d) What is the formula of hexaamminecobalt(III) tetrachloroferrate(III)?

PLAN: We use the rules for writing formulas and names of

coordination compounds.
SOLUTION:
(a) The complex ion is [AlF6]3-. There are six (hexa-) F- ions (fluoro)
as ligands. The complex ion is an anion, so the ending of the
metal name must be changed to –ate. Since Al has only one
oxidation state, no Roman numerals are used.
sodium hexafluoroaluminate
Sample Problem 23.3
(b) There are two ligands, Cl- (chloro) and en (ethylenediamine).
The ethylenediamine ligand already has a numerical prefix in
its name, so we indicate the two en ligands by the prefix bis
instead of di.
The complex ion is a cation, so the metal name is unchanged,
but we need to specify the oxidation state of Co. The counter
ion is NO3-, so the complex ion is [Co(en)2Cl2]+.
Charge of complex ion = charge of metal ion + total charge of ligands
1+ = charge of metal ion + [(2 x 0) + (2 x 1-)]
Charge of metal ion = (+1) – (-2) = +3 or 3+

The ligands must be named in alphabetical order:

dichlorobis(ethylenediamine)cobalt(III) nitrate
Sample Problem 23.3
(c) The central metal ion is written first, followed by the neutral
ligands and then (in alphabetical order) by the negative ligands.

Charge of complex ion = charge of metal ion + total charge of ligands

= (4+) + [(4 x 0) + (1 x 1-) + (1 X 1-)]
= +4 + (-2) = +2 or 2+

We will therefore need two Cl- counter ions to balance the charge on the
complex ion.
[Pt(NH3)4BrCl]Cl2
Sample Problem 23.3
(d) This compound consists of two different complex ions. In the
cation, there are six NH3 ligands and the metal ion is Co3+, so
the cation is [Co(NH3)6]3+.

The anion has four Cl- ligands and the central metal ion is Fe3+,
so the ion is [FeCl4]-.
The charge on the cation must be balanced by the charge on
the anion, so we need three anions for every one cation:

[Co(NH3)6][FeCl4]3
 Name the compound

• The three hydroxides bridge between the two cobalt ions. We

name such compounds from left to right and remember to put a µ
in front of the bridging ligands.
• The oxidation states of the metals could be (III) and (III), (II)
and (IV), (I) and (V), or any other combination adding up to 6, but
even from our brief exposure to cobalt chemistry, you would
probably (and correctly) choose the first alternative.

• The full name of the compound is

triamminecobalt(III)-µ-trihydroxotriamminecobalt(III) nitrate
Write the formula for
tetraamminechromium(III)-µ-amido-µ-hydroxobis
(ethylenediamine)iron(III) sulphate.

The OH− and NH2− are bridging ligands between the cobalt
and iron cations. The overall charge on this huge cation is
4+ (6+ from the two 3+ cations and 2+ from the two 1+
anions). Therefore, there must be two 2+ sulphates in the
formula:
 Classification of Complex
Compounds

1. By the charge of the complex ion:

 Classification of Complex
Compounds
2. By the nature of ligands:
 Concept Check #4.1
1. Name the following coordination compounds.
(a) [Co(H2O)6]Br3
(b) Na2[PtCl4]
(c) [Cr(H2O)5Cl]Cl2
(d) K3[Fe(CN)6]
(e) [Mn(CO)(NH3)5]SO4

(a) Hexaaquacobalt(III) bromide

(b) Sodium tetrachloroplatinate(II)
(c) Pentaaquachlorochromium(III) chloride
(d) Potassium hexacyanoferrate(III)
(e) Pentaamminocarbonylmanganese(II) sulphate
2. Name the following coordination compounds

(a) Tetraaquaplatinum(II) hexachloroplatinate(IV)

(b) Ammonium diaquatetrabromovanadate(III)
(c) Tris(ethylenediamine)cobalt(III)
trioxalatoferrate(III)
(d) Pentacarbonylchloromanganese(I)
(e) sodium hexanitritocobaltate (III)

(a) [Pt(H2O)4][PtCl6]2-
(b) NH4[V(H2O)2Br4]
(c) [Co(en)3][Fe(ox)3]
(d) [Mn(CO)5Cl]+
(e) Na3[Co(ONO)6]
Some Classes of Isomers
Some Classes of Isomers
 Structural Isomerism

• Coordination Isomerism:
▪ Composition of the complex ion varies.
▪ [Cr(NH3)5SO4]Br and [Cr(NH3)5Br]SO4

• Linkage Isomerism:
▪ Composition of the complex ion is the
same, but the point of attachment of at
least one of the ligands differs.
Linkage Isomerism of NO2–
 Linkage (ambidentate)
Isomerism
• A few ligands may bond to the metal through
different atoms.
– SCN- and NO2-
• How would you expect hard acids to bond to the
thiocyanate ligand?
• Solvents can also influence bonding.
– High and low dielectric constants.
• Steric effects of linkage isomerism

• Intramolecular conversion between linkages.

– [Co(NH3)5NO2]+2.
 Stereoisomerism

• Geometrical Isomerism (cis-trans):

▪ Atoms or groups of atoms can assume

different positions around a rigid ring or
bond.

▪ Cis – same side (next to each other)

▪ Trans – opposite sides (across from each

other)
Geometrical (cis-trans) Isomerism for a
Square Planar Compound
(a) cis isomer (b) trans isomer
Geometrical (cis-trans) Isomerism for an
Octahedral Complex Ion
Geometric (cis-trans) isomerism

The cis and trans isomers of [Pt(NH3)2Cl2].

In the cis isomer, identical ligands are adjacent to each other, while
in the trans isomer they are across from each other.

The cis isomer (cisplatin) is an antitumor agent while the trans

isomer has no antitumor effect.
Figure 23.9B Geometric (cis-trans) isomerism.

The cis and trans isomers of [Co(NH3)4Cl2]+.

Note the placement of the Cl- ligands (green spheres).
Separation and Identification of
Isomers
• Geometric isomers can be separated by
fractional crystallization with different
counterions.
– Due to the slightly different shapes of the
isomers.
– The ‘fit’ of the counterion can greatly
influence solubility.
• Solubility is the lowest when the positive and
negative charges have the same size and magnitude
of charges (Basolo).
 Chirality

• Mirror images are nonsuperimposable.

• A molecule can be chiral if it has no rotation-

reflection axes (Sn)

• Chiral molecules have no symmetry elements or

only have an axes of proper rotation (Cn).
– CBrClFI, Tetrahedral molecule (different ligands)
– Octahedral molecules with bidentate or higher
chelating ligands
– Octahedral species with [Ma2b2c2], [Mabc2d2],
[Mabcd3], [Mabcde2], or [Mabcdef]
 Six-Coordinate Octahedral
Complexes
•ML3L3’
– Fac isomers have three
identical ligands on the
same face.
– Mer isomers have three
identical ligands in a
plane bisecting the
molecule.
 Six-Coordinate Octahedral
Complexes
• The maximum number of isomers can be
difficult to calculate (repeats).
• Placing a pair of ligands in the notation
<ab> indicates that a and b are trans to
each other.
• [M<ab><cd><ef>], [Pt<pyNH3><NO2Cl><BrI>]
• How many diastereoisomers in the above
platinum compound (not mirror images)?
• Identify all isomers belonging to Ma3bcd.
Determining the Number of
Isomers
 Determining the Number of
Isotopes
• Bailar method

• With restrictions (such as chelating

agents) some isomers may be
eliminated.

• Determine and identify the number if

isomers.
– [Ma2b2cd] and [M(AA)bcde]
 Combinations of Chelate
Rings
• Propellers and helices
– Left- and right-handed propellers

• Examine the movement of a propeller

required to move it in a certain direction.
– For a left-handed propeller, rotating it ccw
would cause it to move away ().
– For a right-handed propeller, rotating it cw
would cause it to move away (). This is called
‘handedness’. Many molecules possess it.
 Tris(ethylenediamine)cobalt
(III)
• This molecule can be treated like a
three-bladed propeller.
• Look down a three fold axis to
determine the ‘handedness’ of this
complex ion.
– The direction of rotation required to pull
the molecule away from you determines the
handedness ( or ).
• Do this with you molecule set and
rubber bands.
 Determining Handedness
for Chiral Molecules
• Complexes with two or more nonadjacent
chelate rings may have chiral character.
• Any two noncoplanar and nonadjacent chelate
rings can be used.

• Molecules with more than one pair of rings may

require more than one label.
– Ca(EDTA)2+
– Three labels would be required.
– Remember that the chelate rings must be
noncoplanar, nonadjacent, and not connected at the
same atom.
Optical Isomers
Figure 23.10A Optical isomerism in an octahedral complex ion.

Structure I and its mirror image, structure II, are optical

isomers of cis-[Co(en)2Cl2]+.
Figure 23.10B Optical isomerism in an octahedral complex ion.

The trans isomer of [Co(en)2Cl2]+ does not have optical isomers.

Structure I can be superimposed on its mirror image, structure
II.
 Stereoisomerism

• Optical Isomerism:

▪ Isomers have opposite effects on plane-

polarized light.
Unpolarized Light Consists of
Waves Vibrating in Many
Different Planes
 The Rotation of the Plane of
Polarized Light by an Optically
Active Substance
 Optical Activity

• Exhibited by molecules that have non-

superimposable mirror images (chiral
molecules).

• Enantiomers – isomers of
nonsuperimposable mirror images.
 A Human Hand Exhibits a
Nonsuperimposable Mirror Image
 Concept Check #4.2

Does
[Co(en)2Cl2]Cl
[Fe(CO)3Cl3]
exhibit geometrical isomerism?
Yes
Does it exhibit optical isomerism? If
yes, which one does,
Explain.
 Chapter 5 -
Electronic Structure
and Properties
 Bonding in Complex Ions
1. The VSEPR model for predicting structure
generally does not work for complex ions.

▪ However, assume a complex ion with a

coordination number of 6 will have an octahedral
arrangement of ligands.

▪ And, assume complexes with two ligands will be

linear.

▪ But, complexes with a coordination number of 4

can be either tetrahedral or square planar.
 Bonding in Complex Ions

2. The interaction between a metal ion and a

ligand can be viewed as a Lewis acid–base reaction
with the ligand donating a lone pair of electrons
to an empty orbital of the metal ion to form a
coordinate covalent bond.
The interaction between a metal ion and a
ligand can be viewed as a lewis acid-base
reaction
Hybrid Orbitals onCo3+ Can
Accept an Electron Pair from
Each NH3 Ligand
The Hybrid Orbitals Required for
Tetrahedral, Square Planar, and
Linear Complex Ions
 Bonding in coordination
compounds
• Alfred Werner - 1893
• VBT
• Crystal Field Theory
(CFT)
• Modified CFT, known as
Ligand Field Theory
• MOT
Nobel prize 1913
How & Why?
 Valance Bond Theory

Basic Principle
A covalent bond forms when
the orbtials of two atoms
overlap and are occupied by a
pair of electrons that have
the highest probability of
being located between the
nuclei.
Linus Carl Pauling
(1901-1994)
Nobel prizes: 1954, 1962
 Valance Bond Model
Ligand = Lewis base
Metal = Lewis acid
s, p and d orbitals give hybrid orbitals with specific geometries
Number and type of M-L hybrid orbitals determines geometry of the complex

Octahedral
Complex
e.g. [Cr(NH3)6]3+
Tetrahedral e.g. [Zn(OH)4]2- Square Planar e.g. [Ni(CN)4]2-

Limitations of VB theory
Cannot account for colour of complexes
May predict magnetism wrongly
Cannot account for spectrochemical series
 Square Planar

The nickel complex is diamagnetic – which tells us that all the

electrons are paired. A way to explain this, is to have the
unpaired electrons of the Ni2+ ion to pair, leaving behind an
empty d orbital which can then be used in the hybridization.
 Tetrahedral

[Zn(OH)4]2- shows us that when the d orbitals of the metal ion

are filled, the next lowest available (empty) orbitals are the s
and p orbitals of the next quantum number – in this case, the 4s
and 4p orbitals. If 4 ligands are going to come in, all three
empty orbitals will be hybridized together to form sp3
hybridized orbitals.
Crystal Field Theory

400 500 600 800

• The relationship
between colors
and complex
metal ions
 Crystal Field Model
• A purely ionic model for transition metal complexes.
• Ligands are considered as point charge.
• Predicts the pattern of splitting of d-orbitals.
• Used to rationalize spectroscopic and magnetic
properties.
d-orbitals: look attentively along the
axis

Linear combination of
dz2-dx2 and dz2-dy2
Octahedral Field
 Crystal Field Model
• Focuses on the effect of ligands on the energies of the d
orbitals of metals.

Assumptions
1. Ligands are negative point charges.
2. There is no interaction between metal orbitals and ligand
orbitals
3. The d-orbitals on the metal are degenerate in free atom.
However, when a complex is formed the ligands destroy the
degeneracy, splitting the orbitals into different energy
levels.
4. Metal–ligand bonding is entirely ionic:
• strong-field (low–spin): large splitting of d orbitals
• weak-field (high–spin): small splitting of d orbitals
 Octahedral Complexes
• dz2, dx2-y2 point their lobes directly at the point-charge
ligands.

• dxz, dyz, dxy, point their lobes between the point charges.

• Because the negative point-charge ligands repel negatively

charged electrons, the electrons will first fill the d orbitals
farthest from the ligands to minimize repulsions.

• The dxz, dyz, dxy, orbitals (t2g) are at a lower energy in the
octahedral complex than are the dz2, dx2-y2 orbitals (eg),
which are at a higher energy.
An Octahedral Arrangement of Point-Charge
Ligands and the Orientation of the 3d Orbitals
In Octahedral Field

dyz

dz 2

dxz

dx2-y2

dxy
The Energies of the 3d Orbitals for a
Metal Ion in an Octahedral Complex
CFSE
 CFSE

C. F. Splitting of d – orbitals in An octahedral field = Δo or 10 Dqo

 Crystal Field Theory

• According to the Crystal Field Theory, ligands that

have high spin are considered "weak field" and
ligands that have low spin are considered "strong
field." This relates to the colours seen in a
coordination complex.

• High spin ligands induce the absorption of longer

wavelength (lower frequency = lower energy) light
than complexes with low spin ligands since their
respective Δo values are smaller than the electron
pairing energy.
 Crystal Field Theory

• The energy difference, Δo, determines the colour of

the coordination complex.

• According to the spectrochemical series, the high

spin ligands are considered "weak field," and
absorb longer wavelengths of light (weak Δo), while
complexes with low spin ligands absorb light of
greater frequency (high Δo). The colour seen is the
complementary colour of that of the wavelength
absorbed.
 Possible Electron Arrangements in the
Split 3d Orbitals in an Octahedral Complex
of Cr3+

∆o< P 𝑡23 𝑔 𝑒𝑔1 ∆o< P 𝑡24 𝑔

CFSE CFSE
= [3(-0.4)+0.6]∆o = 4(-0.4∆o)
= -0.6∆o = -1.6∆o + P

PARAMAGNETIC P Pairing energy

Ground state Ground state

4−
𝑪𝒓 𝑯𝟐 𝑶 𝟔 𝟐+ 𝐶𝑟 𝐶𝑁 6
 Possible Electron Arrangements in the
Split 3d Orbitals in an Octahedral Complex
of Co3+
Crystal Field Theory: Splitting of
the 5 d orbitals
Consider the response of the energy
of the d orbitals to the approach of 6
negatively charged ligands (a “crystal
field”) along the x, y and z axes of the
metal

The two d orbitals (dx2-y2 and dz2)

eg orbitals
that are directed along the x, y and z
axes are affected more than the
other three d orbitals (dxy, dxz and
dyz)

The result is that the dx2-y2 and

dz2 orbital increase in energy
relative to the dxy, dxz and dyz
orbitals (∆0 is called the “crystal
field energy splitting t2g orbitals
 Crystal field splitting of the 5 d
orbitals by the “crystal field” of 6
e orbitals
g
ligands

Crystal field
splitting

t2g orbitals
Crystal Field Splitting of d orbitals: high spin and
low spin situations for a d5 metal (draw the
diagrams for high and low spin)

Large
splitting: Small
Low spin splitting:
High spin

Net spin = 0 spins Net spin = 5 spins

Diamagnetic Paramagnetic
The d electron configurations of M(II) cations
of the transition metals

Metal Atom Cation (II) Valence electrons

Configuration

Sc [Ar]4s23d1 3d1
Ti [Ar]4s23d2 3d2
V [Ar]4s23d3 3d3
Cr [Ar]4s13d5 3d4
Mn [Ar]4s23d5 3d5
Fe [Ar]4s23d6 3d6
Co [Ar]4s23d7 3d7
Ni [Ar]4s23d8 3d8
Cu [Ar]4s23d9 3d9
Zn [Ar]4s23d10 3d10
Building of weak field, high spin electron
configurations

113
How many unpaired spins in Fe(CN)64- and in Fe(H2O)62+?

What is the charge of Fe in Fe(CN)64- and in Fe(H2O)62+?

Fe2+ in both cases Fe = [Ar]3d64s2; Fe2+ = [Ar]3d6

What kind of ligands are CN- CN- is a strong field ligand and
and H2O? H2O is a weak field ligand

Energy gap larger than

Large splitting advantage due to Hund’s rule
Low spin

Small splitting
Energy gap small;
High spin Hund’s rule applies
 Spectrochemical Series

• Strong–field ligands to weak–field ligands.

(large split) (small split)

CO > CN– > PPh3 > NO2– > phen > bpy > en > NH3 > py > CH3C≡N
> NCS– > H2O > O2– > C2O42– > OH– > F– > N3– > NO2– > Cl– >
SCN– > S2– > Br– > I–

• Magnitude of split for a given ligand increases as the charge on the metal
ion increases.

Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Co3+ < Mo3+ < Rh3+ < Ru3+
< Pd4+ < Ir3+ < Pt4+
• High-spin complexes always have the same number of unpaired
electrons as in a spherical field (free ion), and we therefore do
not need to consider pairing energies for high-spin complexes.

• The values of ΔO for complexes of 4d- and 5d-series metals are

typically higher than for the 3d-series metals due to because the
orbitals are less compact and electron–electron repulsions
correspondingly weaker.

• The Magnitude of ΔO depends on three things։

– Nature of ligands
– Charge on metal ion
– Whether the metal ion is in the 1st, 2nd, or 3rd raw of the
transition elements

• For 3d-metal ions, low-spin complexes commonly occur for

ligands that are high in the spectrochemical series (such as CN−)
and high-spin complexes are common for ligands that are low in
the series (such as F−).
 Magnitude of 
Oxidation state of the metal ion
[Ru(H2O)6]2+ 19800 cm-1
[Ru(H2O)6]3+ 28600 cm-1

Number of ligands and geometry

t < o
t = 4/9o

Nature of the ligand

I-<S2-<SCN-<Cl-<NO3-<N3-<F-<OH-<C2O42-<H2O<…..CN-
<CO
 Crystal Field Splitting Energy (CFSE)
• In Octahedral field, configuration is: t2gx egy
• Net energy of the configuration relative to the
average energy of the orbitals is:
= (-0.4x + 0.6y)O
O = 10 Dq

BEYOND d3

• In weak field: O  P, => t2g3eg1

• In strong field: O  P, => t2g4
• P - paring energy
Ground-state Electronic Configuration,
Magnetic Properties and Colour
 When the 4th electron is assigned it will either go into the
higher energy eg orbital at an energy cost of Do or be
paired at an energy cost of P, the pairing energy.

d4

Strong field = Weak field =

Low spin High spin
(2 unpaired) (4 unpaired)

P < Δo P > Δo

Coulombic repulsion energy and exchange energy

Ground-state Electronic Configuration,
Magnetic Properties and Colour
[Mn(H2O)6]3+
Weak Field Complex
the total spin is 4  ½ = 2
High Spin Complex

[Mn(CN)6]3-
Strong field Complex
total spin is 2  ½ = 1
Low Spin Complex
 Placing electrons in d orbitals
d5 d6 d7

1 u.e. 5 u.e. 0 u.e. 4 u.e. 1 u.e. 3 u.e.

d8 d9 d10

2 u.e. 2 u.e. 1 u.e. 1 u.e. 0 u.e. 0 u.e.

What is the CFSE of [Fe(CN)6]3-?
CN- = s.f.l.
C.N. = 6  Oh Fe(III)  d5 h.s. l.s.
CN 3-
eg eg
CN
NC
Fe + 0.6 oct
NC CN

CN
- 0.4 oct
t2g t2g

CFSE = 5 x - 0.4 oct + 2P = - 2.0 oct + 2P

If the CFSE of [Co(H2O)6]2+ is -0.8 oct, what spin state is it in?

H2O = 6  Oh Co(II)  d7 h.s. l.s.

OH2 2+ eg eg
OH2 + 0.6 oct
H2O
Co
H2O OH2 - 0.4 oct
t2g t2g
OH2

CFSE = (5 x - 0.4 oct) CFSE = (6 x - 0.4 oct)

+ (2 x 0.6 oct) +2P = - 0.8 oct+2P + (0.6 oct) + 3P= - 1.8 oct + P
 The origin of the color of the transition
metal compounds
E2

E h

E1

E = E2 – E1 = h
Ligands influence O, therefore the colour
LFSE for Octahedral Complexes
Ligand-field stabilization
energies for octahedral
complexes
 Example։ 5.1 - Calculating the
LFSE
Determine the LFSE for the following octahedral ions from first
principles and confirm the value matches those in the Table above: (a)
d3, (b) high-spin d5, (c) high-spin d6, (d) low-spin d6, (e) d9.

Answer։ We need to consider the total orbital energy in each case and,
when appropriate, the pairing energy.

(a) A d3 ion has configuration t32g (no pairing of electrons) and

therefore
LFSE = 3 × (−0.4ΔO) = −1.2ΔO.

(b) A high spin d5 ion has configuration t32g e2g (no pairing of
electrons), therefore
LFSE = (3 × −0.4 + 2 × 0.6)ΔO
= 0.
(c) A high-spin d6 ion has configuration t42g e2g with the pairing of
two electrons. However, since those two electrons would be
paired in a spherical field there is no additional pairing energy to
be concerned with. Therefore
LFSE = (4 × −0.4 + 2 × 0.6)ΔO
= −0.4ΔO.

(d) A low-spin d6 ion has configuration t62g with the pairing of three
pairs of electrons. Since one pair of electrons would be paired in
a spherical field, the additional pairing energy is 2P. Therefore
LFSE = 6 × (−0.4ΔO) + 2P
=−2.4ΔO + 2P.

(e) A d9 ion has configuration t62g e3g with the pairing of four pairs
of electrons. Since all four pairs of electrons would be paired in
a spherical field there is no additional pairing energy.
Therefore LFSE = (6 × −0.4 + 3 × 0.6)ΔO
= −0.6ΔO.
Magnetic Properties
 Magnetic measurements
The spin only magnetic moment, μ, of a complex with total spin
quantum number S is
1ൗ
𝜇 = 2 𝑆 𝑆 + 1 2 𝜇𝐵

Where μB is Bohr magneton

S = ½N, where N is the number of unpaired electrons, each
with spin, S = ½

1ൗ
𝜇 = 𝑁 𝑁+2 2 𝜇𝐵

For example, magnetic measurements on a d6 complex easily

distinguish between a high-spin t42g e2g(N = 4, S = 2, μ = 4.90
μB) configuration and a low-spin t62g(N = 0, S = 0, μ = 0)
configuration.
The magnetic moment  of a complex with total
spin quantum number S is:

•  = 2{S(S+1)}1/2 B (B is the Bohr magneton)

• B = eh/4me = 9.274 10-24 J T-1

• Since each unpaired electron has a spin ½,

• S = (½)n, where n = no. of unpaired electrons

•  = {n(n+2)}1/2 B
• In d4, d5, d6, and d7 octahedral complexes, magnetic
measurements can very easily predict weak versus
strong field.
• Tetrahedral complexes - only high spin complexes
result, for t  O.
 n = no. of unpaired electrons
 = {n(n+2)}1/2 B
Ion n S /B Experimental
Calculate
d
Ti3+ 1 1/2 1.73 1.7 – 1.8
V3+ 2 1 2.83 2.7 – 2.9
Cr3+ 3 3/2 3.87 3.8
Mn3+ 4 2 4.90 4.8 – 4.9
Fe3+ 5 5/2 5.92 5.3

Similar Calculation can be done

for Low-spin Complex
 Magnetic Properties

• Strong–field (low–spin):
▪ Yields the minimum number of unpaired
electrons.

• Weak–field (high–spin):
▪ Gives the maximum number of unpaired
electrons.

• Hund’s rule still applies.

 Magnetic measurements

• Compounds are classified as։

❑ diamagnetic if they are repelled by a magnetic field
and
❑ paramagnetic if they are attracted by a magnetic
field.

• The magnitude of the paramagnetism of a complex is

commonly reported in terms of the magnetic dipole
moment it possesses: the higher the magnetic dipole
moment of the complex, the greater the paramagnetism
of the sample.
Gouy balance to
measure the magnetic
susceptibilities
 Example։ 5.2 - Magnetic Moment

1. The magnetic moment of a certain octahedral Co(II)

complex is 4.0 μB. What is its d-electron configuration?

Answer։ We need to match the possible electron

configurations of the complex with the observed magnetic
moment. A Co(II) complex is d7. The two possible
configurations are t52g e2g (high spin, N = 3, S = 3/2) with
three unpaired electrons or t62g e1g (low spin, N = 1, S = 1/2 )
with one unpaired electron. The spin-only magnetic moments
are 3.87μB and 1.73μB, respectively (see Table 20.3 ).

Therefore, the only consistent assignment is the high-spin

configuration t52g e2g.
2. What is the magnetic moment (spin only) of [NiCl4]2-?

Hybridisation is sp3, and it’s a d8, with 2 unpaired electron

𝜇 = 𝑛 𝑛+2 = 2 2 + 2 = 𝟐. 𝟖𝟑𝑩𝑴

3. Determine the magnetic moments of the following

complexes:
FeCl3.6H2O
K3[Fe(CN)6]

FeCl3.6H2O, d5, with 5 unpaired electrons; μ = √5(5+2) =

5.92BM
K3[Fe(CN)6], d5, with 1 unpaired electron; μ = √1(1+2) = 1.73BM
 Concept Check #5.1
1. Estimate the spin-only contribution
to the magnetic moment for each of
the following complexes:

[Co(NH3)6]3+,
[Fe(OH2)6]2+,
[Cr(NH3)6]3+
 Complex Ion Colours

• When a substance absorbs certain wavelengths

of light in the visible region, the color of the
substance is determined by the wavelengths of
visible light that remain.

▪ Substance exhibits the color complementary

to those absorbed.

▪ Solutions containing the hydrated Ti3+ ions

are reddish violet coloured because
yellow/green light is absorbed to excite the
electron. Thus the transmitted light is the
complementary colour red/violet.
 Optical absorption
spectrum of [Ti(OH2)6]3+

The optical absorption

spectrum of the d1
hexaaquatitanium(III) ion,
[Ti(OH2)6]3+. Crystal-field
theory assigns the first
absorption maximum at 493
nm (20 300 cm−1) to the
transition eg ←t2g and
identifies 20 300 cm−1 with
ΔO for the complex.
 Coat of many colours
• Transition metal ions exhibit colours that vary strongly
with the type of ligand used
• Spectrochemical series orders the ligands according to
the degree of crystal field splitting achieved
• An absorption peak of 500 nm corresponds to a
crystal field splitting of:

6.626 × 10−34 𝐽 ∙ 𝑠𝑒𝑐 × 3.00 × 108 𝑚/𝑠𝑒𝑐

𝐸= −9 𝑚
500 × 10
= 3.98 × 10−19 𝐽

On a molar basis:

3.98 × 10−19 𝐽 6.02 × 1023 𝑖𝑜𝑛

∆= ×
𝑖𝑜𝑛 𝑚𝑜𝑙
= 𝟐𝟑𝟗. 𝟓𝟗𝟔 𝒌𝑱/𝒎𝒐𝒍
Calculate ∆ (crystal field splitting E)
Using Ephoton = h = hc/ = ∆

[Ti(H2O)6]3+ has max abs @ 498 nm

What is the CFSE in kJ/mol?

Calculate it!

ℎ𝑐
𝐸𝑝ℎ𝑜𝑡𝑜𝑛 = ℎ𝜈 = =∆
𝜆

ℎ𝑐 6.626 × 10−34 𝐽 ∙ 𝑠𝑒𝑐 × 3.00 × 108 𝑚 ∙ 𝑠𝑒𝑐 −1 −19

∆= = = 3.99 × 10 𝐽
𝜆 498 × 10−9 𝑚

∆= 3.99 × 10−19 𝐽/𝑖𝑜𝑛 × 6.022 × 1023 𝑖𝑜𝑛𝑠/𝑚𝑜𝑙 = 𝟐𝟒𝟎. 𝟐𝟕𝟕𝒌𝑱/𝒎𝒐𝒍

 Complex Ion Colours

• The ligands coordinated to a given metal ion

determine the size of the d–orbital splitting,
thus the color changes as the ligands are
changed.

• A change in splitting means a change in the

wavelength of light needed to transfer
electrons between the t2g and eg orbitals.
 Colour and Magnetic
Behaviour
Most main-group ionic compounds are colourless and
diamagnetic because the metal ion has no unpaired
electrons.

Many transition metal ionic compounds are highly colored

and paramagnetic because the metal ion has one or more
unpaired electrons.

Transition metal ions with a d0 or d10 configuration are

also colourless and diamagnetic.
Crystal Field Theory: The Colour
of Coordination Compounds
The energy gap between the eg
and t2g orbitals, 0, (the crystal
field splitting) equals the energy
of a photon:
h =
0 = h = E

As 0, varies, h will also vary

and the colour of the compound
will change
Absorption of a photon causes a
jump from a t2g to an eg orbital
The spectrochemical series of color and magnetic
properties: weak field (red, high spin), strong field
(violet, low spin)
A d5 electron metal ion

Strong field Weak field

Ligands (violet, low spin) Ligands (red, high spin)
 Colour of complex ions
Colour in an octahedral complex
• When 6 ligands surround a transition metal the ligand lone pair of
electrons interact differently with the different d sub-orbitals.

• The 5 d sub-orbitals split into 2 sets: an upper set of 2 orbitals

(eg) and a lower set of 3 sub-orbitals (t2g). The available number
of d electrons fill these orbitals starting with the lower set.

• If there is a gap in the upper set of orbitals visible light will

excite an electron from a lower to upper orbital. This light will be
removed from the incident light and colour will be seen. If, for
example, red light is absorbed the complex will be blue.

• complexes with 3d10 arrangements are colourless because there is no

gap in the upper set of sub-orbitals e.g. Cu(I) , Zn(II) and Ag(I)
compounds are colourless.
 The color that we see is the color that
is not absorbed, but is transmitted.
The transmitted light is the
complement of the absorbed light.

So if red light is mainly absorbed the

Numbers are nm
color is green; if green light is mainly
absorbed, the color is red.
Figure 23.5 Aqueous oxoanions of transition elements.
+2 +6 +7
Mn2+ MnO42− MnO4−

The highest oxidation state for

Mn equals its group number.

+5 +6 +7
VO43− Cr2O72− MnO4−

Transition metal ions are

often highly colored.
Color of complexes depend on the value of 0 = h = E

0 = h

“red “violet
absorption” absorption”

“looks green” “looks yellow

In real systems there are
regions of different light
absorptions leading to a
wide range of colors
Absorbtion of Visible Light by the
Complex Ion Ti(H2O)63+
 Example 5.3: Colour of Complex
1. An octahedral metal complex absorbs light with wavelength
535 nm. What is the crystal field splitting Δo for the
complex? What colour is it to the eye?

Solution:

ℎ𝑐
Δ𝑜 =
𝜆

6.625 × 10−34 𝐽 ∙ 𝑠𝑒𝑐 × 2.998 × 108 𝑚 ∙ 𝑠𝑒𝑐 −1

∆𝑜 = −9
= 𝟑. 𝟕𝟏𝟐 𝑱
535 × 10 𝑚

Light that is 535 nm is green, and because green light is

absorbed, the complex appears red
2. An aqueous solution of Zn2+ is colourless, that of [Co(en)3]3+
is yellow while that of [CoF6]3− is blue. Explain why.

Solution:
 19.2 Structures of Coordination Complexes: The
ammonia complexes of Co(III) = Co3+

How did Werner deduce the structure of coordination complexes?

Composition Ions released Color

CoCl3.6NH3 3 “free” Cl- ions Orange-Yellow

CoCl3.5NH3 2 “free” Cl- ions Purple

CoCl3.4NH3 1 “free” Cl- ions Green

CoCl3.3NH3 0 “free” Cl- ions Green

In all of these complexes there is no free NH3

(No reaction with acid) 158
 Logic: Cl- is not in coordination sphere; NH3 is in sphere

Compound 1: CoCl3.6NH3 = [Co(NH3)6]3+(Cl-)3 = [Co(NH3)6](Cl)3

Conclude: 3 free Cl- ions, [Co(NH3)6]3+

Compound 2: CoCl3.5NH3 = [Co(NH3)5Cl]2+(Cl-)2 = [Co(NH3)5Cl](Cl)2

Conclude: 2 free Cl- ions, [Co(NH3)5Cl]2+

Compound 3: CoCl3.4NH3 = [Co(NH3)4Cl2]1+(Cl-) = [Co(NH3)4Cl2](Cl)

Conclude: 1 free Cl- ion, [Co(NH3)4Cl2]1+

Compound 4: CoCl3.3NH3 = [Co(NH3)3Cl3]

No free Cl- ions

 Concept Check # 5.2
Which of the following are expected to form
colourless octahedral compounds?
Ti4+ Cr3+ Mn2+
Fe2+ Fe3+ Co2+
Co3+ Ni2+ Cu+
Cu2+ Zn2+ Ag+
There are 4 colorless octahedral compounds. These are either
d10 ions (Zn2+, Cu+, Ag+), or the d0 ion (Ti4+). If electrons cannot
move from one energy level to the next in the energy level
diagram, there is no color absorbed.
Tetrahedral Crystal Field Splitting
In Tetrahedral Field
 Tetrahedral Arrangement
None of the 3d orbitals “point at the ligands”.
• Difference in energy between the split d orbitals is significantly
less.

d–orbital splitting will be opposite to that for the octahedral

arrangement.
• Weak–field case (high–spin) always applies.
 The Crystal Field Diagrams for
Octahedral and Tetrahedral Complexes
 Tetrahedral Arrangement

• The ligand-field splitting parameter in a tetrahedral

complex, ΔT, is less than ΔO, as should be expected
for complexes with fewer ligands, none of which is
oriented directly at the d orbitals (in fact, ΔT ≈ 4/9
ΔO).

• The pairing energy is invariably more unfavourable

than ΔT, and normally only high-spin tetrahedral
complexes are encountered.
LFSE for Tetrahedral Complexes
The d Orbitals in a Tetrahedral
Arrangement of Point Charges
Ligand-Field stabilization energies
for tetrahedral complexes
 Octahedral versus Tetrahedral
Coordination
• Consideration of the LFSE predicts that d3 (chromium(III))
and d8 (nickel(II)) ions strongly prefer an octahedral
geometry over a tetrahedral one; for other configurations
the preference is less pronounced; LFSE has no bearing on
the geometry of d0, high-spin d5, and d10 ions.

• d4 and d9 configurations show a preference for octahedral

complexes (for example Mn(III) and Cu(II)).

• tetrahedral complexes of d1, d2, d6, and d7 ions will not be

too disfavoured; thus V(II) (d2) and Co(II) (d7) form
tetrahedral complexes ([MX4]2-) with chloride, bromide, and
iodide ligands.
 Concept Check # 5.3
Consider the Crystal Field Model (CFM).:

1. Which is lower in energy, d–orbital lobes pointing toward ligands or

between? Why?

2. The electrons in the d–orbitals – are they from the metal or the ligands?

In all cases these answers explain the crystal field model. The molecular
orbital model is a more powerful model and explains things differently.
However, it is more complicated. This is another good time to discuss the role
of models in science.

1. Lobes pointing between ligands are lower in energy because we assume

ligands are negative point charges. Thus, orbitals (with electron
probability) pointing at negative point charges will be relatively high in
energy.

2. The electrons are from the metal.

 Concept Check # 5.3
Consider the Crystal Field Model (CFM).

3. Why would electrons choose to pair up in d–orbitals instead

of being in separate orbitals?

4. Why is the predicted splitting in tetrahedral complexes

smaller than in octahedral complexes?

3. Since some orbitals are higher in energy than others (see "a"), electrons
may actually be lower in energy by pairing up than by jumping up in energy
to be in a separate orbital.

4. In an octahedral geometry there are some orbitals pointing directly at

ligands. Thus, there is a greater energy difference between these (larger
splitting).
 Concept Check # 5.4
Using the Crystal Field Model, sketch possible electron
arrangements for the following. Label one sketch as strong
field and one sketch as weak field.

a) Ni(NH3)62+
b) Fe(CN)63–
c) Co(NH3)63+
a) A d8 ion will look the same as strong field or weak field in an
octahedral complex. In each case there are two unpaired electrons.

b) This is a d5 ion. In the weak field case, all five electrons are
unpaired. In the strong field case, there is one unpaired electron.

c) This is a d6 ion. In the weak field case, there are four unpaired
electrons. In the strong field case, there are no unpaired electrons.
 Concept Check # 5.5

A metal ion in a high–spin octahedral complex has 2

more unpaired electrons than the same ion does in a
low–spin octahedral complex.

What are some possible metal ions for which this

would be true?

Metal ions would need to be d4 or d7 ions.

Examples include Mn3+, Co2+, and Cr2+.
 Concept Check # 5.6

Between [Mn(CN)6]3– and [Mn(CN)6]4– which is more

likely to be high spin? Why?

[Mn(CN)6]4- is more likely to be high spin because

the charge on the Mn ion is 2+ while the
[Mn(CN)6]3- the charge on the Mn ion is 3+. With
a larger charge, there is bigger splitting between
energy levels, meaning strong field, or low spin.
Jahn – Teller Distortion

Jahn–Teller effect : if the ground

electronic configuration of a nonlinear
complex is orbitally degenerate, and
asymmetrically filled, then the
complex distorts so as to remove
the degeneracy and achieve a lower
energy.

Which distortion occurs in practice is

a matter of energetics, not symmetry.
However, because axial elongation
weakens two bonds but equatorial
elongation weakens four, axial
elongation is more common than axial
compression.
Jahn – Teller Distortion
• The filling of dz2 and dx2-y2 is asymmetrical,
the degeneracy is destroyed.

• If the dz2 orbitals contains one electron

more than the dx2-y2 orbitals, the ligand
approaching the z-axis encounter greater
repulsion that the other four (x and y axes)
and this is called tetragonal distortion
elongation.

• If the dx2-y2 contains more electrons than the

dz2 orbitals, the elongation will occur along
the x and y axes and this is called tetragonal
compression.
Examples of significant Jahn-Teller

are found in complexes:

•d4 high spin (weak ligands) Cr(II) and

Mn(III)
▪d7 low spin (strong ligands) Co(II) and
Ni(III)
•d9 (strong or weak ligands) Cu(II) and
Ag(II)
The d Energy Diagrams for Square Planar
Complexes
• A d8 configuration, coupled with a strong crystal
field (strong enough to favour the low-spin, favours
the formation of square-planar complexes. This
tendency is enhanced with the 4d and 5d metals
because of their larger size and the greater ease of
electron pairing.

▪In this configuration the electronic stabilization

energy can more than compensate for any
unfavourable steric interactions. Thus, many square-
planar complexes are found for complexes of the
large 4d 8 and 5d 8 Rh(I), Ir(I), Pt(II), Pd(II),
and Au(III) ions, in which unfavourable steric
constraints have less effect and there is a large
ligand-i eld splitting associated with the 4d- and
5d-series metals.
The d Energy Diagrams for Linear
Complexes Where the Ligands Lie
Along the z Axis
Comparing all 3 ligand
geometries
 Limitation of CFT
1. CFT considers only the metal ion d-orbitals and gives no
consideration at all to other metal orbitals such as s, px, py, and
pz orbitals and the ligand orbitals. Therefore, to explain all the
properties of the complexes dependent on the π-ligand orbitals
will be outside the scope of CFT. CFT does not consider the
formation of π-bonding in complexes.

2. CFT is unable to account satisfactorily for the relative

strengths of ligand, e.g., it gives no explanation as to why H2O
appears in the spectrochemical series as a stronger ligand than
OH-.

3. According to CFT, the bond between the metal and ligand is

purely ionic, It gives no account of the partly covalent nature of
the metal-ligand bonds.
 Transition Metal Complexes
in Biological Molecules

•Metal ion complexes are used in

humans for the transport and
storage of oxygen, as electron-
transfer agents, as catalysts, and as
drugs.
Porphines, hemes, hemoglobin

Photosynthesis: electron transfer

Vitamin B12

205
 Porphines and hemes:
important molecules in living systems

Porphine (C20H14N4)) heme (C34H32N4O4Fe)

 Why do we need to eat d
metals?
Some critical enzymes in our cells are metalloproteins, giant
biolmolecules which contain a metal atom

These metalloproteins control key life processes such as respiration and

protect cells against disease

Hemoglobin is a metalloprotein which contains an iron atom and

transports O2 through out living systems

Vitamin B12, which prevents pernicious anemia, contains a Co atom which

gives the vitamin a red color
The Heme Complex
 Reversible addition of O2 to
Hemoglobin

The mechanism by which oxygen is carried throughout the

body
 Myoglobin
• The Fe2+ ion is
coordinated to
four nitrogen
atoms in the
porphyrin of the
heme (the disk in
the figure) and on
nitrogen from the
protein chain.
• This leaves a 6th
coordination
position (the W)
available for an
oxygen molecule.
Hemoglobin
• Each hemoglobin
has two α chains
and two β
chains, each
with a heme
complex near
the center.
• Each hemoglobin
molecule can
complex with
four O2
molecules.
Hemoglobin and Heme
Coordination compounds are of great importance in biological systems. The
pigment responsible for photosynthesis, chlorophyll, is a coordination
compound of magnesium. Haemoglobin, the red pigment of blood which acts
as oxygen carrier is a coordination compound of iron. Vitamin B12,
cyanocobalamine, the anti–pernicious anaemia factor, is a coordination
compound of cobalt. Among the other compounds of biological importance
with coordinated metal ions are the enzymes like, carboxypeptidase A and
carbonic anhydrase (catalysts of biological systems).
A very important porphine that converts solar
photons into food energy: chlorophyll

Chlorophyll (C55H72N4O5Mg)
Involved in many important biological processes,
including the production of red blood cells

Vitamin B12 (Co[C62H88N13O14P])CN

First-Row Transition Metals and Their
Biological Significance
 Biological Importance of Iron
• Plays a central role in almost all living cells.
• Component of hemoglobin and myoglobin.
• Involved in the electron-transport chain.
Metallurgy

• Process of separating a metal from its ore

and preparing it for use.
• Steps:
▪ Mining
▪ Pretreatment of the ore
▪ Reduction to the free metal
▪ Purification of the metal (refining)
▪ Alloying
The Blast Furnace Used In the Production of Iron
A Schematic of the Open Hearth Process
for Steelmaking
CaCO3 ⎯⎯⎯
→ CaO + CO2
Heat

4Al + 3O2 ⎯⎯
→ 2Al2O3
The Basic Oxygen Process for Steelmaking

• Much faster.
• Exothermic oxidation
reactions proceed so
rapidly that they
produce enough heat to
raise the temperature
nearly to the boiling
point of iron without an
external heat source.
 How does CFT measure up?
I. Colours of Transition Metal Complexes
Why are most transition metal complexes brightly coloured but some aren't?
Why do the colours change as the ligand changes?
Why do the colours change as the oxidation state of the metal changes,
even for complexes of the same ligand?

II. Why do different complexes of the same metal ion in the same oxidation state
have different numbers of unpaired electrons?

Why are there only certain values of the number of unpaired

electrons for a given metal ion?

III. Why do some transition metal ions seem to have a fixed coordination
number and geometry, while other metal ions seem variable?

IV. Why do some metal complexes undergo ligand-exchange reactions

very rapidly and other similar complexes react very slowly, yet this
reaction is thermodynamically favorable?
 The Mond Process
Nickel carbonyl, a gas formed from carbon monoxide and metallic nickel.
Scientific Serendipity
In 1890 Ludwig Mond, was investigating the rapid corrosion of nickel
valves used in apparatus for the Solvay process*, and discovered
Ni(CO)4.

In contrast to many nickel compounds which are usually green solids,

Ni(CO)4 is a colourless, volatile, toxic liquid with a very "organic
character".

He used it as the basis of a method to purify nickel, called the "Mond

process".

Ni reacts with CO (leaving the impurities behind), to form Ni(CO)4.

The Ni(CO)4 is passed through a tower filled with nickel pellets at a high velocity and 400 K.
Pure Ni plates out on the pellets.
* A commercial process for the manufacture of Na2CO3. NH3 and CO2 are passed into a sat’d NaCl(aq) solution to
form soluble (NH4)(HCO3), which reacts with the NaCl to form soluble NH4Cl and solid NaHCO3 if the reactor
temperature is maintained below 15°C. The NaHCO3 is filtered off and heated to produce Na2CO3.
 Chapter 6
Reaction kinetics
and Mechanisms
Formation and Reactions of TM
Complexes

What have we done so far?

1. What is the structure of these compounds?

(Coordination Number, Geometry, Isomerization)

2. What holds these complexes together and how do we study them?

(CFT d-orbital splitting, electronic spectroscopy, MO theory)

But….you can’t study them if you can’t get them…..

How are they made?

 Where do we start?
How about with a Co and Pt complex? [Co(en)2(NO2)2]+, and cis/trans platin.

This is an interesting case:

We start with a Co2+ salt….what is the oxidation state of Co in the product?

Why do we use the Co2+?

Ligand substitution occurs more readily than with Co3+… but why?
2 en O2
CoCl2(aq) {[Co(OH2)6]Cl2} [Co(en)2(NO2)2]+
2NO2-

If we change our starting material we can control stereochemistry…. but why?

[PtCl4]2- + 2NH3 cis-PtCl2(NH3)2

[Pt(NH3)4]2+ + 2Cl- trans-PtCl2(NH3)2

Why do these reactions occur the way they do?

We are going to look at influencing factors and mechanisms.
 Coordination Compound
Reactions

• Goal is to understand reaction mechanisms

• Primarily substitution reactions, most are rapid

Cu(H2O)62+ + 4 NH3 → [Cu(NH3)4(H2O)2]2+ + 4 H2O

but some are slow

[Co(NH3)6]3+ + 6 H3O+ → [Co(H2O)6]3+ + 6 NH4+

 Coordination Compound
Reactions
• Labile compounds - rapid ligand exchange (reaction
half-life of 1 min or less)
• Inert compounds - slower reactions
• Labile/inert labels do not imply stability/instability
(inert compounds can be thermodynamically unstable) -
these are kinetic effects
• In general:
– Inert: octahedral d3, low spin d4 - d6, strong field d8 square
planar

– Intermediate: weak field d8

– Labile: d1, d2, high spin d4 - d6, d7, d9, d10
 Stable vs. Unstable
Inert vs. Labile
When TM ions are dissolved in water the ions form aqua complexes.

UV-Vis, NMR indicate a six-coordinate octahedral species for 1st row TMs.

[M(OH2)6]2+/3+
(neutron diffraction of these species was first reported in 1984)
Given that the ions are not “free” in solution, formation of TM complexes involves
the replacement (substitution) of one ligand with another.

[M(OH2)6]2+/3+ + nL [MLn]x+

That these reactions occur in aqueous solution is VERY important to

numerous disciplines including Inorganic Chemistry, Biochemistry,
Analytical Chemistry, Environmental Chemistry and other applications
 TM Aqua Complexes
An IMPORTANT point about TM-aqua complexes.

The amount of time (residence time) the H2O ligands spends attached
to the TM can vary significantly from metal to metal.

[Cr(OH2)6]3+ and [Co(OH2)6]3+ fail to exchange with 18OH2/17OH2 after several hours.
hours
[Cr/Co16(OH2)6]3+ + large XS 18OH2/17OH2 [Cr/Co18/17(OH2)6]3+

Most other TMs exchange water rapidly.

What does this tell us about formation of TM complexes and what we need to consider?

1. Thermodynamics: When examining thermodynamics of a reaction we are entirely

interested in the start and finish of a reaction. What is the extent of reaction?
Where does the equilibrium lie? How do we investigate this?
Gorxn=Gof,prod-Gof,reacts
2. Kinetics: How fast does a reaction reach equilibrium? This relates directly to the
mechanism.
 Look at the reaction coordinate diagram…
The rate at which one
complex converts into
another is governed by the
height of the activation
Reactants energy barrier that lies
Energy Kinetics between them.

Thermodynamics
Products

Reaction Pathway

The rates of substitution reactions span a very wide range and correlate with
the structures of the complexes; complexes that react quickly are called
labile; those that react slowly are called inert or non-labile.
 Kinetics vs. Thermodynamics
We use terms to describe the Thermodynamic and Kinetic aspects of reactivity.
Thermodynamic. Stable or Unstable

Kinetic. Inert or Labile

An inert compound is not “inert” in the usual sense that no reaction
will occur. Rather, the reaction takes place slower than for labile
compounds
There is NO connection between Thermodynamic
Stability/Instability of a complex and its Lability/Inertness toward
substitution.
For example:
Stable …but labile

[Ni(CN)4]2- + 413CN- ⇌ [Ni(13CN)4]2- + 4CN- t1/2 ~ 30sec.

[Ni(CN)4]2- ⇌ Ni2+(aq) + 4CN-(aq) Keq = 1 x 10-30

Unstable but inert

[Co(NH3)6]3+ + 6H2O ⇌ [Co(OH2)6]3++ 6NH4+ t1/2 ~ days.
Keq = 1 x 1025
 Substitution Reactions

𝑀𝐿𝑛 + 𝐿′ ⇌ 𝑀𝐿𝑛−1 𝐿′ + 𝐿

Labile complexes ⟺ Fast substitution reactions (< few min)

Inert complexes ⟺Slow substitution reactions (>h)

Inert Intermediate Labile

d3, low spin, d4-d6, d8 d8 (high spin) d1, d2, low spin d4-d6, d7-
d10
 Substitution Mechanisms
• Two extremes:
Dissociative (D, low coordination number intermediate)
Associative (A, high coordination number intermediate)
• SN1 or SN2 at the extreme limit
• Interchange - incoming ligand participates in the
reaction, but no detectable intermediate
– Can have associative (Ia) or dissociative (Id)
characteristics
• Reactions typically run under conditions of excess
incoming ligand
• We’ll look briefly at rate laws (details in text), consider
primarily octahedral complexes
Principal mechanisms of ligand
exchange in octahedral
complexes
Dissociative

Associative
The typical form of the reaction
profile of reactions with a
dissociatively activated step: an
associative mechanism, Ad; (b) a
(a) dissociative mechanism, Dd
The typical form of the reaction
profile of reactions with an
interchange mechanism: (a)
associatively activated, Ia ; (b)
dissociatively activated, Id .
Substitution Mechanisms
 Conclusions from these examples.
Stable complexes have a large POSITIVE GoRXN for ligand
substitution and Inert complexes have a large POSITIVE G‡
(activation).
Stability and Coordination Complexes ([MLn]x+)
Typically expressed in terms of an overall formation or stability constant.
(This is Kst on the Chemistry Data sheet you receive with exams)

[MLn ]x +
[M]x+ + nL ⇌ [MLn]x+ K st = x+ n
[M(aq ) ][L]
BUT, this does not occur in one fell swoop!!
Water molecules do not just all fly off and are immediately replaced by nL
ligands.
 x+
[M] x+(aq) + L ⇌ [ML] K1

[ML(n-1)]x+ + L ⇌ [MLn]x+ Kn

Ks are the stepwise formation constants and provide

insight into the solution species present as a function of
[L].
 Stepwise formation constants
These formation constants provide valuable information given that different
species may have VERY DIFFERENT properties…including environmental impact.
Such information provides selective isolation of metal ions from solution
through reaction with ligands.

For formation of divalent alkaline earth

and 3d M2+ TM ions the Irving-
Williams Series holds true.

Ba<Sr<Ca<Mg<Mn<Fe<Co<Ni<Cu>Zn

What is contributing to this trend?

1. Charge to radius ratio.

2. CFSE (beyond Mn2+)
Jahn-Teller Distortion
3. Hard-Soft Acids/Bases
 The Pearson LA/LB
“Hard”/“Soft” Approach
Hard Lewis Bases: high EN, low polarizability, hard to oxidize: O, N, F-
donors (Cl- is borderline).

Soft Lewis Bases: low EN, highly polarizable, easy to oxidize: S, P, I-,
Br-, R-, H- donors.

Hard Lewis Acids: small, highly charged (high ox. State): H+, alkali metal
(M+) and alkaline earth (M2+) cations, Al3+, Cr3+,
BF3.

Soft Lewis Acids: large, low oxidation state: Cu+, Ag+, Au+, Tl+, Hg2+, Pd2+,
Pt2+, BH3

In this model, hard acids “like” hard bases and

soft acids “like” soft bases.
 Chelate Effect
[Ni]2+ + 6 NH3 ⇌ [Ni (NH3)6]2+ log Kst = 8.61
[Ni]2+ + 3 en ⇌ [Ni (en)3]2+ log Kst = 18.28

Both ligands have a N-donor, yet the en complex is 10 orders

of magnitude more stable than the NH3.

This is a general effect that a complex with one (or more) 5 or 5-membered
rings has a greatly enhanced stability relative to the similar complex lacking
rings.

Why is this happening? What’s missing from our equation?

[Ni(OH2)6]2+ + 6 NH3 ⇌ [Ni(NH3)6]2+ + 6H2O log Kst = 8.61

[Ni(OH2)6]2+ + 3 en ⇌ [Ni(en)3]2+ + 6H2O log Kst = 18.28

 Reactions of Coordination
Complexes
The reactions of Coordination Complexes may be divided into three
classes:

i) Substitution at the metal center

ii) Reactions of the coordinated ligands
iii) Oxidation and Reduction reactions at the metal center.

For the purposes of our discussion we will confine our discussion to (i)
For substitution reactions on Octahedral and Square Planar
complexes.

We will only briefly discuss one specific reaction involving a

coordinated ligand.
 Rxns of Octahedral Complexes
Consider ML5X : In this complex there are 5 inert ligands (L) and one labile ligand (X).

For our purposes we will consider the replacement of X with an incoming ligand Y.

ML5X + Y ⟶ ML5Y + X

How might this happen?

We need to look at the molecular components.

What elemental steps will result in this process….

In more technical terms: What is the mechanism of this reaction?

There are Two Extreme Cases

Dissociative Mechanism (D) Associative Mechanism (A)

 Dissociative Mechanism
ML5X + Y ML5Y + X

Step 1. Dissociation of X to yield a 5 coordinate intermediate.

K1
ML5X ML5 + X M-X bond is broken

L L Slow and rate determining

L M L
L M L The rate of D only depends
L L L on the conc. of ML5X
L
Trigonal Bipyramidal Square Pyramidal

Step 2. Coordination of Y to the ML5 intermediate.

K2
ML5 + Y ML5Y This mechanism is independent of [Y]
fast
The rate law for this process is rate = K1[ML5X] (the units of K1 are sec-1)
If we find a reaction follows this rate law we conclude it is dissociative.
 Associative Mechanism
ML5X + Y ML5Y + X

Step 1. Collision of ML5X with Y to yield a 7-coordinate intermediate.

(slow) K1
ML5X + Y ML5XY (slow, rate determining)

X Y
L L
L L
M
L
L M
L X
L Y
L L
Capped Pentagonal
Octahedron Bipyramid
Step 2. Cleavage of the M-X bond. (fast)

ML5XY ML5Y + X (fast)

The rate law for this process is rate = K1[ML5X][Y] (the units of K1 are
sec-1Mole-1)
If we find a reaction follows this rate law we conclude it is associative.
 Telling the difference…
By determining the rate law (uni- vs. bi- molecular) we can
determine the mechanism of the reaction in question.

rate = K1[ML5X] or rate = K1[ML5X][Y]

This is achieved via monitoring the disappearance reactant(s)

and the appearance of product(s) using spectroscopic methods
and variations in reactant concentrations.

This is not always as simple as we see here….

We will discuss one complication.

 Solvents and Water!!
Often experimental conditions “mask” the dependence upon [Y].

When a reaction is carried out in a solvent….the solvent is in HUGE

excess and it is not necessarily “innocent” (it can take a role in the rxn)

What is the concentration of water?

Effectively constant at 55.5M.

Be sure you can determine this!!

Given the excess of water, its concentration remains seemingly constant.

As a result, the influence of the water on the mechanism is “masked”. This
results in a pseudo-first order rate law.
 Solvent and Associative
Processes
H2O
ML5X + Y ML5Y + X

Step 1. Collision of ML5X with Y or H2O to yield a 7-coordinate

intermediate.
Given the [H2O] >>>>[Y] it is much more likely that a collision with H2O will occur.
K1
[ML5X] + H2O [ML5X(O H2)] (slow, rate determining)

Step 2. Cleavage of the M-X bond.

K2
[ML5X(OH2)] [ML5OH2] + X (fast)

Step 3 Formation of the M-Y bond.

K3
[ML5X(OH2)] + Y [ML5OH2] + X (fast)
 Looking at the structures…
L L
L K1
L L L
M + H2O M
L L L L
X X OH2

Rate Law
Rate = [overall rate] = k1[ML5X][H2O]
= {k1[H2O]} [ML5X]
= K [ML5X]

Given the [H2O] is constant the rate appears to follow a pseudo-1st order rate
law.

To determine if the process follows A or D mechanism we need to do other

exps.
 ML6 Preferred Mechanism
Octahedral complexes tend to favor a D mechanism through a 5 -coordinate
intermediate.

[M(OH2)6]X+ +17OH2 [M(OH2)5 17(OH2)] X+

We already discussed that the residence time of H2O varies a lot.

1 x 1010 s-1 to 1 x 10-8 s-1

MX+ K1 (s-1)
As the charge/radius ratio increases the
Cs+ 5x109 rate of water exchange decreases.
Li+ 5x108 What obs. of M2+ and M+ can be made?
Ba2+ 2x109
Be2+ 2x102
 Charge/Radius Ratio
Given the M-OH2 bond strength increases as the charge/radius
ratio increases, data are consistent with a mechanism where the
intermediate was obtained from the cleavage of the M-OH2 bond
and a new M-*OH2 bond is formed quickly.

This is Characteristic of a Dissociative Mechanism

Exceptions to the charge/ratio rule exist:

Ni2+(0.83Å), Cr2+(0.94Å), Cu2+(0.87Å) very similar size

Ni2+(K1= 1 x 104 s-1), Cr2+/Cu2+ (K1= 1 x 109 s-1) very different rates.

Some inert TM ions that exchange H2O very slowly:

Cr3+, LS Co3+ and sqr. planar Pt2+

The inert nature of these complexes made it possible for Werner to work out his
theory.
 Inert/Labile d-electron configurations
Generally, INERT oct. complexes have large CFSE*, specifically
d3, and L.S. d4-d6
Other compounds tend to be labile.
(dividing line labile vs. inert is t1/2 of 1 min. at 25oC)

Inert Complexes Labile Complexes

d1,d2,d7, d8,d9,d10
Octahedral d3 and LS d4,d5,d6
HS d4,d5,d6

Sqr. Planar d8 Pt2+ Ni2+

Pd2+
(intermediate)

This summary applies best for 3d TMs.

If you consider 4d and 5d metals it is found that these metals have greater
CFSE and achieve sigma bonds with better overlap than 3d metals.Hence,
such systems tend to be inert on the above time scale.
Why look at water exchange?
The study of simple water exchange reactions is important and
valuable given the rate at which M(OH2)6X+ aqua ions combine with
other ligands (L) to form other complexes…..

Shows little or no dependence on L

Rates for each metal ion are practically the same as the rate of
exchange for H2O on the same metal ion.

We can use exchange reactions to provide insight into other

substitution reactions.
 Anation Reactions
[M(OH2)6]X+ + X- [M(OH2)5 X] (X-1)+ + H2O

This type of reaction is important as its behavior indicates not only

how new complexes are formed but also where coordinated water is
replaced by X-.

[L5M(OH2)]X+ + X- [L5M X] (X-1)+ + H2O

Generally two observations can be drawn:

1. For a given aqua ion, the rate of anation show little dependence on
the nature of L.
2. The rate constant for anation of a given aqua complex is almost the
same as for H2O exchange.
These are consistent with a dissociative mechanism…..WHY?
Chapter 7 - Redox
Chemistry of
Transition Metal
Complexes
 Transition Metals
CONTENTS
• Aqueous metal ions
• Acidity of hexaaqua ions - stability constants
• Introduction to the reactions of complexes
• Reactions of cobalt
• Reactions of copper
• Reactions chromium
• Reactions on manganese
• Reactions of iron(II)
• Reactions of iron(III)
• Reactions of silver and vanadium
• Reactions of aluminium
Electronic Configuration
 Properties of Transition Metals
• Have large charge/radius ratio
• Hard and have high densities
• High melting and boiling
• From compounds which are often
paramagnetic
• Variable oxidation states
• Form coloured ions and compounds
• Form compounds with profound catalytic
activity
• Form stable complexes
 Reactions of metal ions in
aqueous solution
Metal Aqueous Action of Action of Action of Action of Action of
ion NaOH an excess NH3 (aq) an excess Na2CO3
NaOH (aq) NH3 (aq) (aq)
Iron(II) [Fe(H2O)6] Fe(H2O)4(O No further Fe(H2O)4(O No further FeCO3 (s)
2+ (aq) H)2 (s) change H)2 (s) change Green ppt
Green soln Green ppt Green ppt
goes brown
Copper(II) [Cu(H2O)6]2 Cu(H2O)4(O No further Cu(H2O)4(O No further CuCO3 (s)
+ (aq) H)2 (s) change H)2 (s) change Blue-green
Blue soln Blue ppt Blue ppt ppt
Iron(II) [Fe(H2O)6]3 Fe(H2O)3(O No further Fe(H2O)3(O No further Fe(H2O)3(O
+ (aq) H)3 (s) change H)3 (s) change H)3 (s)
Purple soln Brown ppt Brown- Brown ppt
Yellow- orange ppt CO2
brown evolved
Aluminuium [Al(H2O)6]3 Al(H2O)3(O [Al(OH)4]− Al(H2O)3(O No further Al(H2O)3(O
+
(III) H)3 Colourless H)3 (s) change H)3 (s)
Colourless White ppt solution White ppt White ppt
solution CO2
The Aqueous Chemistry of Ions - Hydrolysis
when salts dissolve in water the ions are stabilised
this is because water molecules are polar
hydrolysis can occur and the resulting solution can become acidic
the acidity of the resulting solution depends on the cation present
the greater the charge density of the cation, the more acidic the solution

cation charge ionic radius reaction with water / pH of chloride

Na 1+ 0.095 nm
Mg 2+ 0.065 nm
Al 3+ 0.050 nm

the greater charge density of the cation...

the greater the polarising power and

the more acidic the solution
The Aqueous Chemistry of Ions - Hydrolysis
when salts dissolve in water the ions are stabilised
this is because water molecules are polar
hydrolysis can occur and the resulting solution can become acidic
the acidity of the resulting solution depends on the cation present
the greater the charge density of the cation, the more acidic the solution

cation charge ionic radius reaction with water / pH of chloride

Na 1+ 0.095 nm dissolves 7
Mg 2+ 0.065 nm slight hydrolysis
Al 3+ 0.050 nm vigorous hydrolysis

the greater charge density of the cation...

the greater the polarising power and

the more acidic the solution
 The Aqueous Chemistry of Ions
Theory aqueous metal ions attract water molecules
many have six water molecules surrounding them
these are known as hexaaqua ions
they are octahedral in shape
water acts as a Lewis Base – a lone pair donor
water forms a co-ordinate bond to the metal ion
metal ions accept the lone pair - Lewis Acids

Acidity as charge density increases, the cation has a greater attraction for water
the attraction extends to the shared pair of electrons in water’s O-H bonds
the electron pair is pulled towards the O, making the bond more polar
this makes the H more acidic (more d+)
it can then be removed by solvent water molecules to form H3O+(aq).
 Hydrolysis - Equations
M2+ ions [M(H2O)6]2+(aq) + H2O(l) ⇌ [M(H2O)5(OH)]+(aq) + H3O+(aq)

the resulting solution will now be acidic as there are more protons in the water
this reaction is known as hydrolysis - the water causes the substance to split up

Stronger bases (e.g. CO32- , NH3 and OH¯ ) can remove further protons...
 Hydrolysis - Equations
M3+ ions [M(H2O)6]3+(aq) + H2O(l) ⇌ [M(H2O)5(OH)]2+(aq) + H3O+(aq)

the resulting solution will also be acidic as there are more protons in the water
this SOLUTION IS MORE ACIDIC due to the greater charge density of 3+ ions

Stronger bases (e.g. CO32- , NH3 and OH¯ ) can remove further protons...
 Hydrolysis of Hexaaqua Ions
Lewis bases can attack the co-ordinated water molecules. Theoretically, a
proton can be removed from each water molecule turning the water from a
neutral molecule to a negatively charged hydroxide ion. This affects the overall
charge on the complex ion.
OH¯ OH¯
[M(H2O)6]2+(aq) [M(OH)(H2O)5]+(aq) H+ [M(OH)2(H2O)4](s)
H+
OH¯ OH¯
[M(OH)2(H2O)4](s) H+ [M(OH)3(H2O)3]¯(aq) H+ [M(OH)4(H2O)2]2-(aq)

OH¯ OH¯
[M(OH)4(H2O)2]2-(aq) [M(OH)5(H2O)]3-(aq) H+ [M(OH)6]4-(aq)
H+

When sufficient protons have been removed the complex becomes

neutral and precipitation of a hydroxide or carbonate occurs.

e.g. M2+ ions [M(H2O)4(OH)2](s) or M(OH)2

M3+ ions [M(H2O)3(OH)3](s) or M(OH)3
 Hydrolysis of Hexaaqua Ions
Lewis bases can attack the co-ordinated water molecules. Theoretically, a proton can be
removed from each water molecule turning the water from a neutral molecule to a
negatively charged hydroxide ion. This affects the overall charge on the complex ion.

OH¯ OH¯
[M(H2O)6]2+(aq) [M(OH)(H2O)5]+(aq) [M(OH)2(H2O)4](s)
H+ H+ Precipitated
OH¯ OH¯
[M(OH)2(H2O)4](s) [M(OH)3(H2O)3]¯(aq) [M(OH)4(H2O)2]2-(aq)
H+ H+

OH¯ OH¯
[M(OH)4(H2O)2 ]2-(aq) [M(OH)5(H2 O)]3-(aq) [M(OH)6]4-(aq)
H+ H+

In some cases, if the base is strong, further protons are removed and the precipitate
dissolves as soluble anionic complexes such as [M(OH)6]3- are formed.

Very weak bases H2O remove few protons

Weak bases NH3, CO32- remove protons until precipitation
Strong bases OH¯ can remove all the protons
 Hydrolysis of Hexaaqua Ions
Lewis bases can attack the co-ordinated water molecules. Theoretically, a proton can be
removed from each water molecule turning the water from a neutral molecule to a
negatively charged hydroxide ion. This affects the overall charge on the complex ion.

OH¯ OH¯
[M(H2O)6]2+(aq) [M(OH)(H2O)5]+(aq) [M(OH)2(H2O)4](s)
H+ H+ Precipitated
OH¯ OH¯
[M(OH)2(H2O)4](s) [M(OH)3(H2O)3]¯(aq) [M(OH)4(H2O)2]2-(aq)
H+ H+

OH¯ OH¯
[M(OH)4(H2O)2 ]2-(aq) [M(OH)5(H2 O)]3-(aq) [M(OH)6]4-(aq)
H+ H+

In some cases, if the base is strong, further protons are removed and the precipitate
dissolves as soluble anionic complexes such as [M(OH)6]3- are formed.

Very weak bases H2O remove few protons

Weak bases NH3, CO32- remove protons until precipitation
Strong bases OH¯ can remove all the protons
 Hydrolysis of Hexaaqua Ions
Lewis bases can attack the co-ordinated water molecules. Theoretically, a proton can be
removed from each water molecule turning the water from a neutral molecule to a
negatively charged hydroxide ion. This affects the overall charge on the complex ion.

OH¯ OH¯
[M(H2O)6]2+(aq) [M(OH)(H2O)5]+(aq) [M(OH)2(H2O)4](s)
H+ H+ Precipitated
OH¯ OH¯
[M(OH)2(H2O)4](s) [M(OH)3(H2O)3]¯(aq) [M(OH)4(H2O)2]2-(aq)
H+ H+

OH¯ OH¯
[M(OH)4(H2O)2 ]2-(aq) [M(OH)5(H2 O)]3-(aq) [M(OH)6]4-(aq)
H+ H+

AMPHOTERIC CHARACTER
Metal ions of 3+ charge have a high charge density and their hydroxides can
dissolve in both acid and alkali.
H+ OH¯
[M(H2O)6]3+(aq) [M(OH)3(H2O)3](s) [M(OH)6]3-(aq)
Soluble Insoluble Soluble
 Stability Constants
Definition :- The stability constant, Kstab, of a complex ion
is the equilibrium constant for the formation of the complex
ion in a solvent from its constituent ions.

In the reaction:

[M(H2O)6]2+(aq) + 6X¯(aq) ⇌ [MX6]4–(aq) + 6H2O(l)

The expression for the stability constant is

𝑀𝑋6 (𝑎𝑞) 4−
𝐾𝑠𝑎𝑏 =
𝑀 𝐻2 𝑂 6 (𝑎𝑞) 2+ 𝑋 − (𝑎𝑞) 6
 Stability Constants
Because ligand exchange involves a series of equilibria, each step in the process has a
different stability constant…

Kstab / dm3 mol-1

[Co(H2O)6]2+(aq) + NH3(aq) [Co(NH3)(H2O)5]2+(aq) + H2O(l) K1 = 1.02 x 10-2

[Co(NH3)(H2O)5]2+(aq) + NH3(aq) [Co(NH3)2(H2O)4]2+(aq) + H2O(l) K2 = 3.09 x 10-2

[Co(NH3)2(H2O)4]2+(aq) + NH3(aq) [Co(NH3)3(H2O)3]2+(aq) + H2O(l) K3 = 1.17 x 10-1

[Co(NH3)3(H2O)3]2+(aq) + NH3(aq) [Co(NH3)4(H2O)2]2+(aq) + H2O(l) K4 = 2.29 x 10-1

[Co(NH3)4(H2O)2]2+(aq) + NH3(aq) [Co(NH3)5(H2O)]2+(aq) + H2O(l) K5 = 8.70 x 10-1 etc

 Stability Constants
Because ligand exchange involves a series of equilibria, each step in the process has a
different stability constant…

Kstab / dm3 mol-1

[Co(H2O)6]2+(aq) + NH3(aq) [Co(NH3)(H2O)5]2+(aq) + H2O(l) K1 = 1.02 x 10-2

[Co(NH3)(H2O)5]2+(aq) + NH3(aq) [Co(NH3)2(H2O)4]2+(aq) + H2O(l) K2 = 3.09 x 10-2

[Co(NH3)2(H2O)4]2+(aq) + NH3(aq) [Co(NH3)3(H2O)3]2+(aq) + H2O(l) K3 = 1.17 x 10-1

[Co(NH3)3(H2O)3]2+(aq) + NH3(aq) [Co(NH3)4(H2O)2]2+(aq) + H2O(l) K4 = 2.29 x 10-1

[Co(NH3)4(H2O)2]2+(aq) + NH3(aq) [Co(NH3)5(H2O)]2+(aq) + H2O(l) K5 = 8.70 x 10-1 etc

The overall stability constant is simply the equilibrium constant for the total reaction.
It is found by multiplying the individual stability constants... k1 x k2 x k3 x k4 ... etc

Kstab or pKstab? For an easier comparison,

the expression pKstab is often used… pKstab = -log10Kstab
 Stability Constants
Because ligand exchange involves a series of equilibria, each step in the process has a
different stability constant…

Kstab / dm3 mol-1

[Co(H2O)6]2+(aq) + NH3(aq) [Co(NH3)(H2O)5]2+(aq) + H2O(l) K1 = 1.02 x 10-2

[Co(NH3)(H2O)5]2+(aq) + NH3(aq) [Co(NH3)2(H2O)4]2+(aq) + H2O(l) K2 = 3.09 x 10-2

[Co(NH3)2(H2O)4]2+(aq) + NH3(aq) [Co(NH3)3(H2O)3]2+(aq) + H2O(l) K3 = 1.17 x 10-1

[Co(NH3)3(H2O)3]2+(aq) + NH3(aq) [Co(NH3)4(H2O)2]2+(aq) + H2O(l) K4 = 2.29 x 10-1

[Co(NH3)4(H2O)2]2+(aq) + NH3(aq) [Co(NH3)5(H2O)]2+(aq) + H2O(l) K5 = 8.70 x 10-1 etc

Summary
• The larger the stability constant, the further the reaction lies to the right
• Complex ions with large stability constants are more stable
• Stability constants are often given as pKstab
• Complex ions with smaller pKstab values are more stable
 Reaction Types
One typical properties of transition elements is their ability to form
complex ions.
Complex ions consist of a central metal ion surrounded by co-ordinated
ions or molecules known as ligands. This can lead to changes in ...

• colour • co-ordination number

• shape • stability to oxidation or reduction

Reaction
types ACID-BASE A-B

LIGAND SUBSTITUTION LS

Ppt
PRECIPITATION
RED OX REDOX
REDOX
 Reaction Types
The examples aim to show typical properties of transition metals and
their compounds.

LOOK FOR...
substitution reactions of complex ions
variation in oxidation state of transition metals
the effect of ligands on co-ordination number and shape
increased acidity of M3+ over M2+ due to the increased charge density
differences in reactivity of M3+ and M2+ ions with OH¯ and NH3
the reason why M3+ ions don’t form carbonates
amphoteric character in some metal hydroxides (Al3+ and Cr3+)
the effect a ligand has on the stability of a particular oxidation state
 Cobalt
Cobalt exists in two stable oxidation states, +2 and +3

The ease of oxidation of cobalt from +2 to +3 depends on the ligand and the pH:
• It is extremely difficult to oxidise cobalt from +2 to +3 in acidic solution.
• It is easier to oxidise Co2+ in alkaline solution using hydrogen peroxide. The
blue Co(OH)2 is oxidized to brown Co(OH)3:

Co(OH)2(s) + OH-(aq) == Co(OH)3(s) + e

H2O2(aq) + 2e == 2OH-(aq)
Overall: 2Co(OH)2(s) + H2O2(aq) → 2Co(OH)3(s)

• In ammoniacal solution it is very easy to oxidise Co2+, and it is oxidized when

left to stand in air. The straw Co(NH3)62+ is oxidised to the brown Co(NH3)63+
(the solution gets darker):

Co(NH3)62+(aq) == Co(NH3)63+(aq) + e
O2(g) + 2H2O(l) + 4e → 4OH-(aq)
Overall: 4Co(NH3)62+(aq) + O2(g) + 2H2O(l) → 4Co(NH3)63+(aq) + 4OH-(aq)
 Reactions of Cobalt(II)
• aqueous solutions contain the pink, octahedral hexaaquacobalt(II) ion
• hexaaqua ions can also be present in solid samples of the hydrated salts
• as a 2+ ion, the solutions are weakly acidic but protons can be removed by
bases... A-B

OH¯ [Co(H2O)6]2+(aq) + 2OH¯(aq) → [Co(OH)2(H2O)4](s) + 2H2O(l)

pink, octahedral blue / pink ppt. soluble in XS
NaOH

All hexaaqua ions precipitate a hydroxide with OH¯(aq). Some re-dissolve in

excess NaOH.
 Reactions of Cobalt(II)
[Co(H2O)6]2+(aq) + 2NH3(aq) → [Co(OH)2(H2O)4](s) + 2NH4+(aq)
A-B
ALL hexaaqua ions precipitate a hydroxide with NH3 (aq). It removes
protons.

Some hydroxides redissolve in excess NH3(aq) as ammonia substitutes as a

ligand.

[Co(OH)2(H2O)4](s) + 6NH3(aq) → [Co(NH3)6]2+(aq) + 4H2O(l) + 2OH¯(aq)

LS
 Reactions of Cobalt(II)
but ... ammonia ligands make the Co(II) state unstable. Air oxidises
Co(II) to Co(III)
OX

[Co(NH3)6]2+(aq) → [Co(NH3)6]3+(aq) + e¯
yellow / brown octahedral red / brown octahedral

CO32- [Co(H2O)6]2+(aq) + CO32-(aq) → CoCO3(s) + 6H2O(l)

mauve ppt. Ppt

Hexaaqua ions of metals with charge 2+ precipitate a carbonate but

heaxaaqua ions with a 3+ charge don’t.
 Reactions of Cobalt(II)
Cl¯ [Co(H2O)6]2+(aq) + 4Cl¯(aq) → [CoCl4]2-(aq) + 6H2O(l) LS
pink, octahedral blue, tetrahedral

• Cl¯ ligands are larger than H2O

• Cl¯ ligands are negatively charged - H2O ligands are neutral
• the complex is more stable if tetrahedral - less repulsion between ligands
• adding excess water reverses the reaction
Cobalt
 Reactions of Copper(II)
Aqueous solutions of copper(II) contain the blue, octahedral
hexaaquacopper(II) ion. Most substitution reactions are similar to cobalt(II).

OH¯ [Cu(H2O)6]2+(aq) + 2OH¯(aq) → [Cu(OH)2(H2O)4](s) + 2H2O(l)

blue, octahedral pale blue ppt.
insoluble in XS NaOH A-B

NH3 [Cu(H2O)6]2+(aq) + 2NH3(aq) → [Cu(OH)2(H2O)4](s) + 2NH4+(aq)

blue ppt. soluble in excess NH3
A-B

then [Cu(OH)2(H2O)4](s) + 4NH3(aq) → [Cu(NH3)4(H2O)2]2+(aq) + 2H2O(l) +

2OH¯(aq) royal blue
LS
NOTE THE FORMULA

CO32- [Cu(H2O)6]2+(aq) + CO32-(aq) → CuCO3(s) + 6H2O(l) Ppt

blue ppt.
 Reactions of Copper(II)

Cl¯ [Cu(H2O)6]2+(aq) + 4Cl¯(aq) → [CuCl4]2-(aq) + 6H2O(l)

yellow, tetrahedral
LS

• Cl¯ ligands are larger than H2O and are charged

• the complex is more stable if the shape changes to tetrahedral
• adding excess water reverses the reaction

I¯ 2Cu2+(aq) + 4I¯(aq) → 2CuI(s) + I2(aq)

off - white ppt. REDOX

• a redox reaction
• used in the volumetric analysis of copper using sodium
thiosulphate
 Reactions of Copper(I)

The aqueous chemistry of copper(I) is unstable compared to copper(0)

and copper (II).

Cu+(aq) + e¯ → Cu(s) E° = + 0.52 V

Cu2+(aq) + e¯ → Cu+(aq) E° = + 0.15 V
subtracting 2Cu+(aq) → Cu(s) + Cu2+(aq) E° = + 0.37 V

This is an example of DISPROPORTIONATION where one species is

simultaneously oxidised and reduced to more stable forms. This
explains why the aqueous chemistry of copper(I) is very limited.

Copper(I) can be stabilised by formation of complexes.

 Chromium
Chromium forms stable ions in three different oxidation states, +2, +3
and +6.

The +6 chromium complexes can be readily interconverted using acid

and alkali:
2CrO42-(aq) + 2H+(aq) → Cr2O72-(aq) + H2O(l)
Cr2O72-(aq) + 2OH-(aq) → 2CrO42-(aq) + H2O(l)

a) In acidic solution:

All chromium (VI) compounds can be reduced to the +3 and then the +2
oxidation state by strong reducing agents such as zinc in acid solution.
The chromium is first reduced to the +3 oxidation state:

Cr2O72-(aq) + 14H+(aq) + 6e → 2Cr3+(aq) + 7H2O(l)

Zn(s) → Zn2+(aq) + 2e
Overall: Cr2O72-(aq) + 14H+(aq) + 3Zn(s) → 2Cr3+(aq) + 7H2O(l) +
3Zn2+(aq)
 Chromium
It is then further reduced:

Cr3+(aq) + e → Cr2+(aq)
Zn(s) → Zn2+(aq) + 2e
Overall: Zn(s) + 2Cr3+(aq) → Zn2+(aq) + 2Cr2+(aq)

The colour change observed on adding zinc in acid solution to

dichromate ions is orange (Cr2O72-) to green (Cr3+) to blue (Cr2+).

Other, milder reducing agents will reduce the +6 oxidation state to +3

but no further. Fe2+ is an important example:

Fe2+(aq) → Fe3+(aq) + e
Overall: Cr2O72-(aq) + 14H+(aq) + 6Fe2+(aq) → 2Cr3+(aq) + 7H2O(l) +
6Fe3+(aq)

This reaction can be used in titrations to determine the concentration

of Fe2+ ions in a sample.
 Chromium
b) In alkaline solution

In alkaline solution, it is possible to oxidise the +3 oxidation state to

the +6 oxidation state.

The chromium ion forms the [Cr(OH)6]3- complex in alkaline conditions.

This complex can be oxidized to the +6 oxidation state by adding H2O2.
Hydrogen peroxide, which is a reducing agent in acidic solution, is an
oxidizing agent in alkaline solution.

[Cr(OH)6]3-(aq) + 2OH-(aq) → CrO42-(aq) + 4H2O(l) + 3e

H2O2(aq) + 2e → 2OH-(aq)
2[Cr(OH)6]3-(aq) + 3H2O2(aq) → 2CrO42-(aq) + 8H2O(l) + 2OH-(aq)

The green [Cr(OH)6]3- ion is oxidised to the yellow CrO42- ion in alkaline
solution.
 Chromium
b) In alkaline solution

In alkaline solution, it is possible to oxidise the +3 oxidation state to the +6

oxidation state.

The chromium ion forms the [Cr(OH)6]3- complex in alkaline conditions. This
complex can be oxidized to the +6 oxidation state by adding H2O2. Hydrogen
peroxide, which is a reducing agent in acidic solution, is an oxidizing agent in
alkaline solution.
[Cr(OH)6]3-(aq) + 2OH-(aq) → CrO42-(aq) + 4H2O(l) + 3e
H2O2(aq) + 2e → 2OH-(aq)
2[Cr(OH)6]3-(aq) + 3H2O2(aq) → 2CrO42-(aq) + 8H2O(l) + 2OH-(aq)

The green [Cr(OH)6]3- ion is oxidised to the yellow CrO42- ion in alkaline solution.

The relative tendency of species to undergo oxidation and reduction often

depends dramatically on the pH of the solution. The interconversion of the
chromium (III) and chromium (VI) oxidation states is an important example.
In general, oxidation is favoured by alkaline conditions and reduction is favoured
by acidic conditions.
 Reactions of Chromium(III)
Chromium(III) ions are typical of M3+ ions in this block.
Aqueous solutions contain the violet, octahedral hexaaquachromium(III) ion.

OH¯ [Cr(H2O)6]3+(aq) + 3OH¯(aq) ——> [Cr(OH)3(H2O)3](s) + 3H2O(l) A-B

violet, octahedral green ppt. soluble in XS NaOH

As with all hydroxides the precipitate reacts with acid

[Cr(OH)3(H2O)3](s) + 3H+(aq) ——> [Cr(H2O)6]3+(aq) A-B

being a 3+ hydroxide it is AMPHOTERIC as it dissolves in excess alkali

[Cr(OH)3(H2O)3](s) + 3OH¯(aq) ——> [Cr(OH)6]3-(aq) + 3H2O(l) A-B

green, octahedral
 Reactions of Chromium(III)
2 [Cr(H2O)6]3+(aq) + 3CO32-(aq) → 2[Cr(OH)3(H2O)3](s) + 3H2O(l) + 3CO2(g)

A-B
• The carbonate is not precipitated but the hydroxide is.
• high charge density of M3+ makes the solution too acidic to form the
carbonate
• CARBON DIOXIDE IS EVOLVED.

[Cr(H2O)6]3+(aq) + 3NH3(aq) → [Cr(OH)3(H2O)3](s) + 3NH4+(aq)

green ppt. soluble in XS NH3 A-B
• With EXCESS AMMONIA, the precipitate redissolves

[Cr(OH)3(H2O)3](s) + 6NH3(aq) → [Cr(NH3)6]3+(aq) + 3H2O(l) + 3OH¯(aq)

LS
 Reactions of Chromium(III)
Oxidation:
In the presence of alkali, Cr(III) is unstable and can be oxidised to
Cr(VI)

2Cr3+(aq) + 3H2O2(l) + 10OH¯(aq) → 2CrO42-(aq) + 8H2O(l)

green yellow OX

Acidification of the yellow chromate will produce the orange

dichromate(VI) ion

Reduction:
Chromium(III) can be reduced to the less stable chromium(II) by zinc
in acid RED

2 [Cr(H2O)6]3+(aq) + Zn(s) → 2 [Cr(H2O)6]2+(aq) + Zn2+(aq)

green blue
 Reactions of Chromium(VI)
Occurrence dichromate (VI) Cr2O72- orange

chromate (VI) CrO42- yellow

Interconversion dichromate is stable in acid solution

chromate is stable in alkaline solution

in alkali Cr2O72-(aq) + 2OH¯(aq) ⇌ 2CrO42-(aq) + H2O(l)

in acid 2CrO42-(aq) + 2H+(aq) ⇌ Cr2O72-(aq) + H2O(l)

 Oxidation Reactions Of
Chromium(VI)
Being in the highest oxidation state (+6), chromium(VI) will be an oxidising
agent.

In acidic solution, dichromate is widely used in both organic (oxidation of

alcohols) and inorganic chemistry.

It can also be used as a volumetric reagent but with special indicators as its
colour change (orange to green) makes the end point hard to observe.

Cr2O72-(aq) + 14H+(aq) + 6e¯ → 2Cr3+(aq) + 7H2O(l) [ E° = +1.33 V ]

orange green

• Its E° value is lower than that of Cl2 (1.36V) so can be used in the presence
of Cl¯ ions.
• MnO4¯ (E° = 1.52V) oxidises chloride in HCl so must be acidified with
sulphuric acid.
• Chromium(VI) can be reduced back to chromium(III) using zinc in acid
solution
 Manganese
Manganese can exist in a number of oxidation states, but is most stable
in an oxidation state of +2, +4 or +7

The MnO4- ion is a powerful oxidising agent:

MnO4-(aq) + 8H+(aq) + 5e → Mn2+(aq) + 4H2O(l)

It can therefore be used to determine reducing agents.

In the +7 oxidation state it exists as the intense purple ion MnO4−. This
can be reduced to the pale pink Mn2+ by Fe2+ in acidic solution:

MnO4-(aq) + 8H+(aq) + 5e → Mn2+(aq) + 4H2O(l)

Fe2+(aq) → Fe3+(aq) + 2e
Overall: MnO4-(aq) + 8H+(aq) + 5Fe2+(aq) → Mn2+(aq) + 4H2O(l) +
5Fe3+(aq)
 Reactions of Manganese(VII)
• in its highest oxidation state therefore Mn(VII) will be an oxidising
agent
• occurs in the purple, tetraoxomanganate(VII) (permanganate) ion
(MnO4¯)
• acts as an oxidising agent in acidic or alkaline solution

Acidic: MnO4¯(aq) + 8H+(aq) + 5e¯ → Mn2+(aq) + 4H2O(l)

E° = + 1.52 V

N.B. Acidify with dilute H2SO4 NOT dilute HCl

Alkaline: MnO4¯(aq) + 2H2O(l) + 3e¯ → MnO2(s) + 4OH¯(aq)

E° = + 0.59 V
 Volumetric use of Manganate(VII)
Potassium manganate(VII) in acidic (H2SO4) solution is extremely useful for
carrying out redox volumetric analysis.

MnO4¯(aq) + 8H+(aq) + 5e¯ → Mn2+(aq) + 4H2O(l) E° = + 1.52 V

It must be acidified with dilute sulphuric acid as MnO4¯ is powerful enough to

oxidise the chloride ions in hydrochloric acid.

It is used to estimate iron(II), hydrogen peroxide, ethanedioic (oxalic) acid

and ethanedioate (oxalate) ions. The last two titrations are carried out above
60°C due to the slow rate of reaction.

No indicator is required; the end point being the first sign of a permanent
pale pink colour.

MnO4¯(aq) + 8H+(aq) + 5Fe2+(aq) → Mn2+(aq) + 5Fe3+(aq) + 4H2O(l)

this means that moles of Fe2+ = 5

moles of MnO4¯ 1
 Iron

Iron exists in two common oxidation states, +2 (Fe2+) and +3 (Fe3+).

In aqueous solution, the Fe is readily oxidised from Fe2+ to Fe3+:

Fe2+(aq) → Fe3+(aq) + e

The Fe2+ ion is thus a reducing agent. Concentrations of Fe3+ in solution

can be determined by titration with oxidising agents.
 Reactions of Iron(II)
When iron reacts with acids it gives rise to iron(II) (ferrous) salts. Aqueous
solutions of such salts contain the pale green, octahedral hexaaquairon(II) ion

OH¯ [Fe(H2O)6]2+(aq) + 2OH¯(aq) → [Fe(OH)2(H2O)4](s) + 2H2O(l)

pale green dirty green ppt.
A-B
it only re-dissolves in very conc. OH¯ but...
it slowly turns a rusty brown colour due to oxidation by air to iron(III)
increasing the pH renders iron(II) unstable.

Fe(OH)2(s) + OH¯(aq) → Fe(OH)3(s) + e¯

dirty green rusty brown OX

NH3 Iron(II) hydroxide precipitated, insoluble in excess ammonia

A-B
CO32- Off-white coloured iron(II) carbonate, FeCO3, precipitated
Ppt
 Reactions of Iron(II)

Volumetric: Iron(II) can be analysed by titration with potassium

manganate(VII) in acidic (H2SO4) solution. No indicator is required.

MnO4¯(aq) + 8H+(aq) + 5Fe2+(aq) → Mn2+(aq) + 5Fe3+(aq) + 4H2O(l)

this means that:

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐹𝑒 2+ 5
=
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑀𝑛𝑂4 − 1
 Reactions of Iron(III)
Aqueous solutions contain the yellow-green, octahedral hexaaquairon(III) ion

OH¯ [Fe(H2O)6]3+(aq) + 3OH¯(aq) ——> [Fe(OH)3(H2O)3](s) + 3H2O(l) A-B

yellow rusty-brown ppt. insoluble in XS

CO32- 2[Fe(H2O)6]3+(aq) + 3CO32-(aq) ——> 2[Fe(OH)3(H2O)3](s) + 3H2O(l) + 3CO2(g)

rusty-brown ppt.
A-B
The carbonate is not precipitated but the hydroxide is; the high
charge density of M3+ makes the solution too acidic to form a carbonate
CARBON DIOXIDE EVOLVED.

NH3 [Fe(H2O)6]3+(aq) + 3NH3(aq) ——> [Fe(OH)3(H2O)3](s) + 3NH4+(aq)

rusty-brown ppt. insoluble in XS
A-B

SCN¯ [Fe(H2O)6]3+(aq) + SCN¯(aq) ——> [Fe(SCN)(H2O)5]2+(aq) + H2O(l)

blood-red colour LS
Very sensitive; BLOOD RED COLOUR confirms Fe(III). No reaction with
Fe(II)
 REACTIONS OF SILVER(I)
• aqueous solutions contains the colourless, linear, diammine silver(I) ion
• formed when silver halides dissolve in ammonia

eg AgCl(s) + 2NH3(aq) ——> [Ag(NH3)2]+(aq) + Cl¯(aq)

[Ag(SO3)2]3- Formed when silver salts are dissolved in sodium thiosulphate "hypo" solution.
Important in photographic fixing. Any silver bromide not exposed to light is
dissolved away leaving the black image of silver as the negative.

AgBr + 2S2O32- ——> [Ag(S2O3)2]3- + Br¯

[Ag(CN)2]¯ Formed when silver salts are dissolved in sodium or potassium cyanide
the solution used for silver electroplating

[Ag(NH3)2]+ Used in Tollen’s reagent (SILVER MIRROR TEST)

Tollen’s reagent is used to differentiate between aldehydes and ketones.
Aldehydes produce a silver mirror on the inside of the test tube
Formed when silver halides dissolve in ammonia - TEST FOR HALIDES
 REACTIONS OF VANADIUM
Reduction using zinc in acidic solution shows the various oxidation states of vanadium.

Vanadium(V) VO2+(aq) + 2H+(aq) + e¯ ——> VO2+(aq) + H2O(l)

yellow blue

Vanadium(IV) VO2+(aq) + 2H+(aq) + e¯ ——> V3+(aq) + H2O(l)

blue blue/green

Vanadium(III) V3+(aq) + e¯ ——> V2+(aq)

blue/green lavender
 OXIDATION & REDUCTION - A SUMMARY
Oxidation
• complex transition metal ions are stable in acid solution
• complex ions tend to be less stable in alkaline solution
• in alkaline conditions they form neutral hydroxides and/or anionic complexes
• it is easier to remove electrons from neutral or negatively charged species
• alkaline conditions are usually required

e.g. Fe(OH)2(s) + OH¯(aq) ——> Fe(OH)3(s) + e¯

Co(OH)2(s) + OH¯(aq) ——> Co(OH)3(s) + e¯
2Cr3+(aq) + 3H2O2(l) + 10OH¯(aq) ——> 2CrO42-(aq) + 8H2O(l)

• Solutions of cobalt(II) can be oxidised by air under ammoniacal conditions

[Co(NH3)6]2+(aq) ——> [Co(NH3)6]3+(aq) + e¯

 OXIDATION & REDUCTION - A SUMMARY
Oxidation
• complex transition metal ions are stable in acid solution
• complex ions tend to be less stable in alkaline solution
• in alkaline conditions they form neutral hydroxides and/or anionic complexes
• it is easier to remove electrons from neutral or negatively charged species
• alkaline conditions are usually required

e.g. Fe(OH)2(s) + OH¯(aq) ——> Fe(OH)3(s) + e¯

Co(OH)2(s) + OH¯(aq) ——> Co(OH)3(s) + e¯
2Cr3+(aq) + 3H2O2(l) + 10OH¯(aq) ——> 2CrO42-(aq) + 8H2O(l)

• Solutions of cobalt(II) can be oxidised by air under ammoniacal conditions

[Co(NH3)6]2+(aq) ——> [Co(NH3)6]3+(aq) + e¯

Reduction
• Zinc metal is used to reduce transition metal ions to lower oxidation states
• It acts in acid solution as follows... Zn(s) ——> Zn2+(aq) + 2e¯
e.g. it reduces iron(III) to iron(II)
vanadium(V) to vanadium (IV) to vanadium(III)
 REACTIONS OF ALUMINIUM
• aluminium is not a transition metal as it doesn’t make use of d orbitals
• BUT, due to a high charge density, aluminium ions behave as typical M3+ ions
• aqueous solutions contain the colourless, octahedral hexaaquaaluminium(III) ion

OH¯ [Al(H2O)6]3+(aq) + 3OH¯(aq) ——> [Al(OH)3(H2O3](s) + 3H2O(l) A-B

colourless, octahedral white ppt. soluble in XS NaOH
As with all hydroxides the precipitate reacts with acid

[Al(OH)3(H2O)3](s) + 3H+ (aq) ——> [Al(H2O)6]3+(aq) A-B

being a 3+ hydroxide it is AMPHOTERIC and dissolves in excess alkali

[Al(OH)3(H2O)3](s) + 3OH¯(aq) ——> [Al(OH)6]3-(aq) + 3H2O(l) A-B

colourless, octahedral

CO32- 2 [Al(H2O)6]3+(aq) + 3CO32-(aq) ——> 2[Al(OH)3(H2O)3](s) + 3H2O(l) + 3CO2(g)

As with 3+ ions, the carbonate is not precipitated but the hydroxide is. A-B

NH3 [Al(H2O)6]3+(aq) + 3NH3(aq) ——> [Al(OH)3(H2O)3](s) + 3NH4+(aq) A-B

white ppt. insoluble in XS NH3