Dr.

Paul Charlesworth
Michigan Technological University
Dr. Paul Charlesworth
Michigan Technological University
Chapt er
Chapt er
20
20
Transition Elements and
Coordination Chemistry
Transition Elements and
Coordination Chemistry
Chemistry 4th Edition
McMurry/Fay
Chemistry 4th Edition
McMurry/Fay
Chapter 20 Slide 2
Prentice Hall 2004
Transition Metal Properties 02 Transition Metal Properties 02
Chapter 20 Slide 3
Prentice Hall 2004
Transition Metal Properties 04 Transition Metal Properties 04
Relative Densities:
Chapter 20 Slide 4
Prentice Hall 2004
Transition Metal Properties 04 Transition Metal Properties 04

Oxidation States:
Oxidation States:
Chapter 20 Slide 5
Prentice Hall 2004
Transition Metal Properties 05 Transition Metal Properties 05
Oxidation States: With the exception of Cu, first
row solid transition metals are more easily oxidized
than hydrogen.
Chapter 20 Slide 6
Prentice Hall 2004
Transition Metal Properties 06 Transition Metal Properties 06
Oxidation States: Most
transition metal oxidation
states are brightly colored.
Manganese is shown left to
right:
Mn
2+
Mn
3+
Mn
4+
Mn
6+
Mn
7+
Chapter 20 Slide 7
Prentice Hall 2004
Coordination Compounds 01 Coordination Compounds 01
Coordination compounds are species in which a
central metal ion (or atom) is attached to a group of
surrounding molecules or ions by coordinate
covalent bonds.
Surrounding groups are called Ligands.
Central metal is a Lewis acid.
Ligand is a Lewis base.
The number of ligand donor atoms surrounding the
central metal is called the coordination number.
Chapter 20 Slide 8
Prentice Hall 2004
Coordination Compounds 02 Coordination Compounds 02
Coordinate bond:
Coordination Sphere: is the central metal and
surrounding ligands. The square brackets separate
the complex from counter ions such as SO
4
2
.
H
H
H
H
H
H
H
H
+
H
H
H
H
Ag
+
(aq)
2
Ag
+
[Ag(NH
3
)
2
]
2
SO
4
Chapter 20 Slide 9
Prentice Hall 2004
Coordination Compounds 03 Coordination Compounds 03
Charge of a complex is the sum of the charges on
central metal and ligands.
1) What is the oxidation number for [Co(NH
3
)
5
Cl](NO
3
)
2
?
2) A complex ion contains a Cr
3+
bound to four H
2
O
molecules and two Cl

ions. Write its formula.

[Cu(NH
3
)
4
]
2+
+2
4 (0)
+2
= +
Chapter 20 Slide 10
Prentice Hall 2004
Coordination Compounds 04 Coordination Compounds 04
Geometries:
Chapter 20 Slide 11
Prentice Hall 2004
Ligands 01 Ligands 01
Monodentate ligands bond using the electron
pairs of a single atom.
Bidentate ligands bond using the electron pairs of
two atoms.
Polydentate ligands bond using the electron pairs
of many atoms. This group includes bidentate.
Polydentate ligands are also known as chelating
agents.
Chapter 20 Slide 12
Prentice Hall 2004
Ligands 02 Ligands 02
Chapter 20 Slide 13
Prentice Hall 2004
Ligands 03 Ligands 03
Chapter 20 Slide 14
Prentice Hall 2004
Ligands 04 Ligands 04
EDTA
4
is commonly added
to food products such as
commercial salad dressings.
EDTA
4
is often used to treat
heavy metal poisoning such
as Hg
2+
, Pb
2+
, and Cd
2+
.
EDTA
4
bonds to Pb
2+
, which
is excreted by the kidneys as
[Pb(EDTA)]
2
.
Chapter 20 Slide 15
Prentice Hall 2004
Ligands 05 Ligands 05
(a) and (b) represent bidentate ligands bound to cobalt.
(c) and (d) represent a hexadentate ligand bound to cobalt.
Chapter 20 Slide 16
Prentice Hall 2004
Isomers are compounds that have the same formula but a
different atomic arrangement.
Isomers 01 Isomers 01
Chapter 20 Slide 17
Prentice Hall 2004
Isomers 02 Isomers 02
Constitutional Isomers: Have different
connections among their constituent atoms.
Ionization Isomers differ in that the anion is bonded to
the metal ion. Compare [Co(NH
3
)
5
Br]SO
4
(violet
compound with CoBr bond), and [Co(NH
3
)
5
SO
4
]Br (red
compound with CoSO
4
bond).
Linkage Isomers form when a ligand can bond through
two different donor atoms. Consider [Co(NH
3
)
5
NO
2
]
2+
which is yellow with the CoNO
2
bond and red with the
CoONO bond.
Chapter 20 Slide 18
Prentice Hall 2004
Isomers 03 Isomers 03
[Co(NH
3
)
5
NO
2
]
2+
, Linkage isomers.
Chapter 20 Slide 19
Prentice Hall 2004
Isomers 04 Isomers 04
Diastereoisomers (geometric) have the same
connections among atoms but different spatial
orientations of the metalligand bonds.
a)cis isomers have identical ligands in adjacent corners
of a square.
b)trans isomers have identical ligands across the
corners from each other.
Chapter 20 Slide 20
Prentice Hall 2004
Isomers 05 Isomers 05
Geometric Isomers of Pt(NH
3
)
2
Cl
2
: In the cis
isomer, atoms are on the same side. In the trans
isomer, atoms are on opposite sides.
Chapter 20 Slide 21
Prentice Hall 2004
Isomers 06 Isomers 06
Geometric Isomers of [Co(NH
3
)
4
Cl
2
]Cl:
Chapter 20 Slide 22
Prentice Hall 2004
Enantiomers are stereoisomers of molecules or
ions that are nonidentical mirror images of each
other.
Objects that have handedness are said to be
chiral, and objects that lack handedness are said
to be achiral.
An object or compound is achiral if it has a
symmetry plane cutting through the middle.
Isomers 07 Isomers 07
Chapter 20 Slide 23
Prentice Hall 2004
Isomers 08 Isomers 08
Chapter 20 Slide 24
Prentice Hall 2004
Enantiomers have identical properties except
for their reaction with other chiral substances
and their effect on plane-polarized light.
Enantiomers are often called optical isomers;
their effect on plane-polarized light can be
measured with a polarimeter.
Isomers 09 Isomers 09
Chapter 20 Slide 25
Prentice Hall 2004
Isomers 10 Isomers 10
Plane-polarized light is obtained by passing
ordinary light through a polarizing filter.
In a polarimeter the plane-polarized light is passed
though a chiral solution and the polarization plane
measured with an analyzing filter.
If the plane rotates to the right it is dextrorotatory.
If the plane rotates to the left it is levorotatory.
Equal amounts of each are racemic.
Chapter 20 Slide 26
Prentice Hall 2004
Bonding in Complexes 01 Bonding in Complexes 01
Bonding Theories attempt to account for the
color and magnetic properties
of transition metal complexes.
Ni
2+
Cu
2+
Ni
2+
Cu
2+
Zn
2+
Zn
2+
Co
2+
Co
2+
Solutions of [Ni(H
2
O)
6
]
2+
,
[Ni(NH
3
)
6
]
2+
, & [Ni(en)
3
]
2+
Chapter 20 Slide 27
Prentice Hall 2004
Bonding in Complexes 02 Bonding in Complexes 02
The color of any substance is related to the
wavelength(s) of light absorbed by the substance.
h
EXCITED STATE
GROUND STATE
E
2
E
1
=
hc
E
Chapter 20 Slide 28
Prentice Hall 2004
Bonding in Complexes 03 Bonding in Complexes 03
Valence Bond Theory predicts metal complex
bonding arises from overlap of filled ligand orbitals
and vacant metal orbitals.
Resulting bond is a coordinate covalent bond.
Chapter 20 Slide 29
Prentice Hall 2004
Bonding in Complexes 04 Bonding in Complexes 04
Complex geometry can be linked to five main
orbital hybridization processes.
Chapter 20 Slide 30
Prentice Hall 2004
Bonding in Complexes 05 Bonding in Complexes 05
Tetrahedral Geometry: Gives [CoCl
4
]
2
three
unpaired electrons, which makes it paramagnetic
and attracted by magnets.
Chapter 20 Slide 31
Prentice Hall 2004
Bonding in Complexes 06 Bonding in Complexes 06
Square Planar Geometry: Gives [Ni(CN)
4
]
2
all
paired electrons, which makes it diamagnetic and
weakly repelled by magnets.
Chapter 20 Slide 32
Prentice Hall 2004
Bonding in Complexes 07 Bonding in Complexes 07
Octahedral sp
3
d
2
Geometry: Gives [CoF
6
]
3
four
unpaired electrons, which makes it paramagnetic
and is called a high-spin complex.
Chapter 20 Slide 33
Prentice Hall 2004
Bonding in Complexes 08 Bonding in Complexes 08
Octahedral d
2
sp
3
Geometry: Gives [Co(CN)
6
]
3
paired electrons, which makes it diamagnetic and is
called a low-spin complex.
Chapter 20 Slide 34
Prentice Hall 2004
Bonding in Complexes 09 Bonding in Complexes 09
The difference between sp
3
d
2
and d
2
sp
3
hybrids
lies in the principal quantum number of the d
orbital.
In sp
3
d
2
hybrids, the s, p, and d orbitals have the same
principal quantum numberHigh Spin.
In d
2
sp
3
hybrids, the principal quantum number of the d
orbitals is one less than s and p orbitalsLow Spin.
A complexs magnetic properties determine which
hybrid is being used.
Chapter 20 Slide 35
Prentice Hall 2004
Bonding in Complexes 10 Bonding in Complexes 10
Crystal Field Theory is a model that helps explain
why some complexes are high spin and some are
low spin.
Crystal Field Theory views bonding in complexes
as the result of electrostatic interactions and
considers the effect of ligand charges on energies
of metal ion d orbitals.
Crystal Field Theory uses no covalent bonds.
Chapter 20 Slide 36
Prentice Hall 2004
Bonding in Complexes 11 Bonding in Complexes 11
CFT Octahedral
Complexes
Chapter 20 Slide 37
Prentice Hall 2004
Bonding in Complexes 12 Bonding in Complexes 12
d-electron to ligand-electron repulsions affect d-orbital
energy levels.
d
z
2 and d
x
2
y
2 orbitals
point at the ligands
and have higher
energies than other
d-electrons.
This energy gap () is called crystal field splitting.
Chapter 20 Slide 38
Prentice Hall 2004
Bonding in Complexes 13 Bonding in Complexes 13
The crystal field splitting energy () corresponds to light
wavelengths in the visible region of the spectrum.
[Ti(H
2
O)
6
]
3+
contains a single d-electron in lower energy
orbitals. 500 nm light absorption promotes the d-electron.
Chapter 20 Slide 39
Prentice Hall 2004
Bonding in Complexes 14 Bonding in Complexes 14
Absorption spectra of different complexes indicate the
crystal field splitting energy depends on the ligands nature.
For Ni
2+
complexes increases as the ligand changes from
H
2
O to NH
3
to ethylenediamine (en).
Chapter 20 Slide 40
Prentice Hall 2004
In general, the crystal field splitting energy
increases as the ligand varies in the following
order.
This is known as the spectrochemical series.
Ligands which lead to small values of are called
weak-field ligands. Those which lead to large
values of are called strong-field ligands.
Bonding in Complexes 15 Bonding in Complexes 15
I

< Br

< Cl

< F

< H
2
O < NH
3
< en < CN

Increasing value of
Chapter 20 Slide 41
Prentice Hall 2004
Bonding in Complexes 16 Bonding in Complexes 16
Crystal Field Splitting can also account for magnetic
properties in terms of high- and low-spin complexes.
Weak-field ligands lead to high-spin paramagnetic systems.
Strong-field ligands lead to low-spin diamagnetic systems.