Chapter 19 Transition Metals and Coordination Chemistry

Chapter 19 Transition Metals and
Coordination Chemistry
1
Chapter 19, J.Ren, 2021
Calcite
(containing Fe) Aqueous solutions containing metal ions:
Co2+, Mn2+, Cr3+, Fe3+, Ni2+
Rhodochrosite
(containing MnCO3)
Chapter 19, J.Ren, 2021 2

Minerals formed due to people’s activity may mark Anthropocene epoch
Researchers catalog more than 200 human-influenced minerals
Bluelizardite [Na7(UO2)(SO4)4Cl·2H2O] has

been found only in the Blue Lizard Mine in
Utah. A simonkolleite [Zn5(OH)8Cl2·H2O] sample
was discovered on a piece of copper ore
from a mine in Maricopa County, Ariz.
The latest evidence that people are refashioning Earth is written not in the sky, where
carbon dioxide levels are rising, nor in the acidifying ocean, but in stone. Geologists
have identified about 200 minerals that formed due to the hustle and bustle of human
activity. Many of these unintentionally formed minerals appeared on Earth during the
past two centuries, a blip in the timescale of thousands to millions of years that
geologists typically work with. 3
C&E News Volume 95 Issue 15 | pp. 21-22
Chapter 19, J.Ren, 2021 Issue Date: April 10, 2017
Transition elements on the periodic table

Electron configuration Sc-Zn
5
The First and the Third Ionization Energy
Plots of the first (red dots) and third (blue dots) ionization
energies for the first-row transition metals
Third ionization
energy is much
Third ionization energy higher due to
ejecting 3d
electron
First ionization energy
6
Atomic radii of the 3d, 4d, and 5d transition series
• There is a general decrease in size from left to right across each series.
• There is a significant increase in radii in going from the 3d to the 4d metals
• The 4d and 5d metals are remarkably similar in size.
Lanthanide contraction:
The steady decrease in the atomic radii of the lanthanide elements
when going from left to right across the periodic table (electrons are8
filling the 4f orbitals). Chapter 19, J.Ren, 2021
Self-Reading
The First-Row Transition Metals
Example: nickel compounds

Coordination Compounds
[Co(NH3)6]Cl3
Complex ion: Co(NH3)63+

Metal Ion and Ligands
note
[Co(NH3)6]Cl3

Coordination Number
Coordination number:
The number of bonds formed by the metal ion to ligands in
the complex ion.

Dissolving in water
When dissolves in water, the coordination compounds behave
like ionic salts.

Geometry of complex ions
Ligand arrangements for coordination numbers 2, 4, and 6
14
Type of Ligands
A neutral molecule or ion having a lone pair electron that can be used to form
a bond to a metal ion.
Monodentate ligands H2O, NH3, HO–, Cl–

Bidentate ligands
Polydentate ligands
15
16
Example: bidentate and polydentate complexes
[Co(en)3]3+ [CoEDTA]2-
EDTA in
personal care
products

Nomenclature for Coordination Complexes
1) Overall name order: cation before anion
2) Name order in complex ion: Ligands first, in
alphabetical order, then metal ion
3) Name of ligands:
a) An “o” is added to the root name of an anion, eg. chloro
b) For a neutral molecule, the name of the molecule is
used.
18
4) Numbering of ligands-use prefix
Simple ligands:
1(mono), 2 (di), 3 (tri), 4 (tetra), 5 (penta), 6 (hexa)
Complex ligands:
Bis-, tris-, tetrakis-,….
5) Oxidation states of metal ion:
use Roman number (I, II, III,…)
6) Metal ion in anionic complex:

use Latin name (ate)
7) When more than one type of ligands is present, ligands are

named in alphabetical order (prefixes do not affect the
order) 19
20
Examples:
Pentaamminechlorocobalt(III) Chloride
Potassium hexacyanoferrate(III)
Bis(ethylenediamine)dinitroiron(III) sulfate
Common names:
[Fe(CN)6]4- ferrocyanide
[Fe(CN)6]3- ferricyanide Chapter 19, J.Ren, 2021
21
Examples:
Give the structures of the following compounds
Triamminebromoplatinum(II) chloride
Ans: [Pt(NH 3)3Br]Cl
Answer
Potassium hexafluorocobaltate(III)
Ans: K3Answer
[CoF6]
Pentaaquachlorochromium(III) chloride
Ans: [CrCl(H 2O)5]Cl2
Answer

Examples:
Give the systematic names for the following compounds
[CoCl(NO2)(NH3)4]Cl
Ans:
Tetraamminechloronitrocobalt(III)
Answer chloride
[Co(NH3)6] [Cr(CN)6]
Ans:
Hexaamminecobalt(III) hexacyanochromate(III)
Answer

Isomerism (Isomers)
Substances that have the same formulas, but differ in their
structures and properties
Two main types of isomerism

Structural Isomers:
Same formula, but differ in connectivity
• a) Coordination isomers
• b) Linkage isomers
Stereoisomers:
Same formula, but differ in spatial arrangements of atoms.
• a) Geometric isomers (cis-trans isomers)
• b) Optical isomers
Classes of isomers
25
Coordination Isomers (Isomerism)
The formula is the same, but the composition of the
complex ions varies.
Pentaamminesulfatochromium(III) bromide
Pentaamminebromochromium(III) sulfate

Linkage Isomers (Isomerism)
The composition of the complex ions is the same, but
the point of attachment differs
[Co(NH3)4(NO2)Cl]Cl vs. [Co(NH3)4(ONO)Cl]Cl
Tetraamminechloronitrocobalt(III) chloride
Tetraamminechloronitritocobalt(III) chloride
N-linkage O-linkage
(Yellow) (Red)
Geometric Isomers (cis-trans isomers)
A group of atoms can assume different positions around
a rigid ring or bond
cis-diamminedichloroplatinum(II)
trans-diamminedichloroplatinum(II)
The cis isomer of trans isomer of

Pt(NH3)2Cl2 (yellow). Pt(NH3)2Cl2 (pale yellow).

Examples: cis-trans isomers
trans [Co(NH3)4Cl2] cis [Co(NH3)4Cl2]

Examples
Tell the relationship between the two structures: are they
isomers?
NH3 NH3
Cl NH3
Pt
vs Pt
Cl NH3 Cl
Cl
NH3 NH3 Cl NH3

Pt Pt
vs
Cl NH3 NH3 NH3
Sketch all possible geometrical isomers for [CoCl(ox)(NH3)3]

Optical Isomerism
Chiral objects:
Objects that are nonsuperimposable on their mirror
images.
Achiral objects:
Objects that are superimposable on their mirror
images.
Optical isomers:
• Molecules that are nonsuperimposable mirror images.
• Optical isomers have opposite effects on plane-
polarized light.

Chirality (Handness)
Human hand has a nonsuperimposed mirror image
32
Superimposed vs. nonsuperimposed mirror image
Achiral object
Chiral object
33
Chiral vs. Achiral Objects

Optical Isomers
Molecules that are nonsuperimposable mirror images
Isomers I and II of Co(en)33+ are nonsuperimposable mirror images
35
Ordinary Light vs. Plane-Polarized Light
Propagation of a Light Beam
Ordinary light
Ordinary light Plane-polarized light

The Properties of Optical Isomers
Optical isomers (right-handed vs. left-handed isomers) can
rotate the plane-polarized light in equal but opposite directions.
Rotation of the plane of polarized light by an optically active

substance.

Exercise: Isomerism
• Tell whether the following pairs of compounds are coordination isomers,
linkage isomers, geometric isomers (cis-trans), optical isomers, or the
same compound CN
NH3 NH3 CN
Cl Cl
Cl NH3 Cl NH3 Cl CN
Pt
Co Co Pt
NC OH2
Cl ONO Cl Cl OH2
ONO
OH2 H2O
NH3 NH3
Geometric Answer
(cis-trans) isomers Optical
Answer isomers
N N
N N N
H3N
Co Co
N N N NH3
Br Br
Same compound Linkage isomers

Answer
Answer
Coordination
Answer isomers Optical isomers
Answer
• Draw all possible geometric isomers of [CoCl2(ox)(NH3)2]–. Which of them
also have an optical isomer? Draw the structures.
38
Examples (Exercise): Isomerism
• Draw all possible geometric isomers of [CoCl2(ox)(NH3)2]–. Which of them
also have an optical isomer? Draw the structures.
39
Bonding in Complex Ions:
The Localized Electron Model
Set of six d2sp3 hybrid orbitals
on Co3+ • The VSEPR model can be
used to predict the geometry
of complex ions
• The interaction between a
metal ion and a ligand can
d2sp3 be viewed as a Lewis acid-
base reaction.
• The LE model is rarely used
today because it cannot
predict important properties
of complex ions, such as
magnetism and color.

Bonding in Complex Ions:
The Crystal Field Model
• The ligands can be approximated by negative point charge
and the metal-ligand bonding is entirely ionic.
• The model focuses on the interactions (repulsions) between

ligands and the d-orbitals of the metal ion.
• The electron-electron repulsion between d-orbitals and

ligands will increase the d-orbital energy.

The d-Orbitals of the Metal Ion
Five degenerate d-orbitals (same energy)

The Crystal Field Model
Octahedral Complex
Stronger
repulsion
Higher energy
Weaker
repulsion
Lower energy

Energy Diagram of the Octahedral Complex
Energies of the 3d orbitals
for a metal ion in a octahedral complex.
Δ:
crystal field splitting
(d-orbital splitting)
44
The d-Orbital Splitting
The d-orbital splitting can explain the color and the magnetism
of complex ions for the first row transition metals.
Strong field: if the splitting produced by the ligand is large

• The electrons will largely occupy the lower energy t2g orbitals.
Weak field: if the splitting produced by the ligand is small
• The electrons will occupy all possible orbitals.
The d-orbital splitting depends on the type of the ligands and

also the charge of the metal. Higher charge produces larger
splitting.
Spectrochemical Series:
The arrangement of ligands in order of their ability to produce
d-orbital splitting:
CN – > NO2 – > en > NH3 > H2O > OH – > F – > Cl – > Br – > I– 45
Examples: d-Orbital Splitting
The split 3d orbitals of an octahedral complex of Co3+
Strong field Weak field

Low-spin (paired electrons) High-spin (unpaired electrons)
46
Diamagnetic Paramagnetic Chapter 19, J.Ren, 2021
Examples: d-Orbital Splitting
The complex ion [Fe(CN)6]3- has one unpaired electron.
Predict the d-orbital splitting.
Predict the d-orbital splitting and the unpaired electrons for

the following complex ions:
[Cr(CN)6]4- [MnF6]2-
[Co(H2O)6]2+ (H2O is a low-field ligand)

Color of Complex Ions
Aqueous solutions containing metal ions:
Co2+, Mn2+, Cr3+, Fe3+, Ni2+

Visible Spectrum
High Energy Low Energy

Short wave length Long wave length

Color Theory
Primary colors Secondary colors
Combination of two primary colors
Complementary colors
Each secondary color is a
complementary color of
one of the primary colors
Opposite colors are complementary 50
Color of Complex Ions
[Ti(H2O)6]3+ is violet
Violet is a complementary color of yellow-green
The yellow-green light was absorbed

The violet light was transmitted
51
Complementary colors
52
Examples: Color of Complex Ions
Explain the color change for the following process:
n NH3
[Cr(H2O)6]Cl3 [Cr(NH3)6]Cl3
violet yellow
The complex ions of Zn2+ are all colorless, even their d-orbital splittings
are correct for absorbing visible wavelengths. Give a reasonable
explanation.

Tetrahedral Complex
Weaker
repulsion
Lower energy
Stronger
repulsion
Higher energy
None of the 3d-orbitals points at the ligands. The d-orbital splitting is

smaller in tetrahedral complexes than that in octahedral complexes.

Crystal field diagrams for octahedral and
tetrahedral complexes
Octahedral Complex Tetrahedral Complex
55
(a) Crystal field diagram for a square planar complex
(b) crystal field diagram for a linear complex
Square Planar Complex Linear Complex
56
Examples: Tetrahedral vs. Square Planar
The complex ion, [Ni(CN)4]2-, is diamagnetic. Predict
whether the compound would be tetrahedral or square
planar.

The Molecular Orbital Model [ML6]n+
Mn+ L6
Crystal Field Model

The Molecular Orbital Model
[CoF6]3- [Co(NH3)6]3+

The Biological Significance
60
The heme complex
The heme complex

in which an Fe2+ ion
is coordinated to
four nitrogen atoms
of a planar
porphyrin ligand.
61
Representation of the Hemoglobin Structure
Iron and oxygen-binding protein found in blood
62
Representation of the Myoglobin Molecule
Iron and oxygen-binding protein in the muscle tissue
63

Chapter 19 Transition Metals and Coordination Chemistry

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Chapter 19 Transition Metals and

Chapter 19, J.Ren, 2021 2

Bluelizardite [Na7(UO2)(SO4)4Cl·2H2O] has

Chapter 19, J.Ren, 2021 4

First ionization energy

Example: nickel compounds

Chapter 19, J.Ren, 2021 9

Complex ion: Co(NH3)63+

Chapter 19, J.Ren, 2021 10

Chapter 19, J.Ren, 2021 11

Chapter 19, J.Ren, 2021 12

Chapter 19, J.Ren, 2021 13

Monodentate ligands H2O, NH3, HO–, Cl–

Chapter 19, J.Ren, 2021 17

6) Metal ion in anionic complex:

7) When more than one type of ligands is present, ligands are

Chapter 19, J.Ren, 2021 22

Chapter 19, J.Ren, 2021 23

Two main types of isomerism

Chapter 19, J.Ren, 2021 26

The cis isomer of trans isomer of

Chapter 19, J.Ren, 2021 28

trans [Co(NH3)4Cl2] cis [Co(NH3)4Cl2]

Chapter 19, J.Ren, 2021 29

NH3 NH3 Cl NH3

Sketch all possible geometrical isomers for [CoCl(ox)(NH3)3]

Chapter 19, J.Ren, 2021 30

Chapter 19, J.Ren, 2021 31

Chapter 19, J.Ren, 2021 34

Ordinary light Plane-polarized light

Chapter 19, J.Ren, 2021 36

Rotation of the plane of polarized light by an optically active

Chapter 19, J.Ren, 2021 37

Same compound Linkage isomers

Chapter 19, J.Ren, 2021 40

• The model focuses on the interactions (repulsions) between

• The electron-electron repulsion between d-orbitals and

Chapter 19, J.Ren, 2021 41

Five degenerate d-orbitals (same energy)

Chapter 19, J.Ren, 2021 42

Chapter 19, J.Ren, 2021 43

Strong field: if the splitting produced by the ligand is large

The d-orbital splitting depends on the type of the ligands and

Strong field Weak field

Predict the d-orbital splitting and the unpaired electrons for

[Co(H2O)6]2+ (H2O is a low-field ligand)

Chapter 19, J.Ren, 2021 47

Chapter 19, J.Ren, 2021 48

High Energy Low Energy

Chapter 19, J.Ren, 2021 49

The yellow-green light was absorbed

Chapter 19, J.Ren, 2021 53

None of the 3d-orbitals points at the ligands. The d-orbital splitting is

Chapter 19, J.Ren, 2021 54

Chapter 19, J.Ren, 2021 57

Crystal Field Model

Chapter 19, J.Ren, 2021 58

Chapter 19, J.Ren, 2021 59

The heme complex

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