TRO3 Lecture 24

Chemistry: A Molecular Approach, 1st Ed.
Nivaldo Tro
Chapter 24
Transition
Metals and
Coordination
Compounds
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
2007, Prentice Hall
Gemstones
the colors of rubies and emeralds are both due
to the presence of Cr3+ ions the difference lies
in the crystal hosting the ion
Some Al3+ ions
in Al2O3 are
replaced by
Cr3+
Tro, Chemistry: A Molecular App
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Some Al3+ ions

in
Be3Al2(SiO3)6
are replaced by
Cr3+
2
Properties and Electron Configuration

of Transition Metals
the properties of the transition metals are similar to
each other
and very different tot he properties of the main group metals

high melting points, high densities, moderate to very hard,
and very good electrical conductors
in general, the transition metals have two valence
electrons we are filling the d orbitals in the shell

below the valence
Group 1B and some others have 1 valence electron due to
promotion of an electron into the d sublevel to fill it
form ions by losing the ns electrons first, then the (n 1)d

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Atomic Size
the atomic radii of all
the transition metals
are very similar
small increase in size
down a column

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Ionization Energy
the first ionization
energy of the
transition metals
slowly increases
across a series
third transition series
slightly higher 1st IE
trend opposite to
main group elements
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Electronegativity
the electronegativity of
the transition metals

slowly increases across
a series
except for last element in
the series
electronegativity
slightly increases down

the column
trend opposite to main
group elements

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Oxidation States
often exhibit multiple oxidation states
vary by 1
highest oxidation state is group number for 3B to 7B

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Coordination Compounds
when a complex ion combines with counterions to
make a neutral compound it is called a coordination

compound
the primary valence is the oxidation number of the
metal
the secondary valence is the number of ligands bonded
to the metal
coordination number
coordination number range from 2 to 12, with the most

common being 6 and 4
CoCl36H2O = [Co(H2O)6]Cl3

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Coordination Compound

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Complex Ion Formation

complex ion formation is a type of Lewis acidbase reaction
a bond that forms when the pair of electrons is
donated by one atom is called a coordinate
covalent bond

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Ligands with Extra Teeth

some ligands can form more than one coordinate
covalent bond with the metal atom
lone pairs on different atoms that are separate enough

so that both can reach the metal
chelate is a complex ion containing a

multidentate ligand
ligand is called the chelating agent

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12
EDTA
a Polydentate Ligand

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13
Complex Ions with Polydentate Ligands

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Geometries in Complex Ions

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15
Naming Coordination Compounds

1) determine the name of the noncomplex ion
2) determine the ligand names and list them in
3)
4)
alphabetical order
determine the name of the metal cation
name the complex ion by:
1) name each ligand alphabetically, adding a prefix in front of

each ligand to indicate the number found in the complex ion
2) follow with the name of the metal cation
5) write the name of the cation followed by the name of

the anion

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Common Ligands

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Common Metals found in

Anionic Complex Ions

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Isomers
Structural isomers are molecules that have the
same number and type of atoms, but they are
attached in a different order
Stereoisomers are molecules that have the same
number and type of atoms, and that are attached
in the same order, but the atoms or groups of
atoms point in a different spatial direction
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20
Linkage Isomers

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Geometric Isomers
geometric isomers are stereoisomers that differ
in the spatial orientation of ligands
fac-mer isomerism
isomerismininoctahedral
octahedral
square-planar
complexes
complexes
complexes
MA
MAMA
cis-trans
3B
4B
32 2B2

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Ex. 24.5 Draw the structures and label the type

for all isomers of [Co(en)2Cl2]+
the ethylenediamine ligand (en = H2NCH2CH2NH2) is
bidentate
each Cl ligand is monodentate
octahedral
MA4B2

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[Co(en)3]3+
Optical Isomers
optical isomers are
stereoisomers that are
nonsuperimposable mirror
images of each other

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Ex 24.7 Determine if the cis-trans isomers of

[Co(en)2Cl2]+ are optically active
draw the mirror

image of the
given isomer
and check to
see if they are
superimposable
cis trans
isomer
isomer
mirroridentical
image istononsuperimposable
its mirror image
nooptical
opticalisomers
isomerism
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Bonding in Coordination Compounds

Valence Bond Theory
bonding take place when the filled atomic
orbital on the ligand overlaps an empty atomic
orbital on the metal ion
explain geometries well, but doesnt explain
color or magnetic properties

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Bonding in Coordination Compounds

Crystal Field Theory
bonds form due to the attraction of the electrons on the
ligand for the charge on the metal cation

electrons on the ligands repel electrons in the
unhybridized d orbitals of the metal ion
the result is the energies of orbitals the d sublevel are
split
the difference in energy depends the complex and kinds
of ligands
crystal field splitting energy
strong field splitting and weak field splitting

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Splitting of d Orbital Energies due to

Ligands in a Octahedral Complex

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Strong and Weak Field Splitting

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Complex Ion Color

the observed color is the complimentary color of
the one that is absorbed

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Complex Ion Color and

Crystal Field Strength
the colors of complex ions are due to electronic
transitions between the split d sublevel orbitals
the wavelength of maximum absorbance can be
used to determine the size of the energy gap
between the split d sublevel orbitals
Ephoton = h = hc/ =

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Ligand and
the strength of the crystal field depends in large
part on the ligands
strong field ligands include: CN > NO2 > en > NH3
weak field ligands include H2O > OH > F > Cl >
Br > I
crystal field strength increases as the charge on

the metal cation increases
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Magnetic Properties and

the electron configuration of the metal ion with split d
orbitals depends on the strength of the crystal field

the 4th and 5th electrons will go into the higher energy dx2y2 and dz2 if the field is weak and the energy gap is small
leading to unpaired electrons and a paramagnetic
complex
the 4th thru 6th electrons will pair the electrons in the dxy,
dyz and dxz if the field is strong and the energy gap is large
leading to paired electrons and a diamagnetic complex
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Low Spin & High Spin Complexes
diamagnetic
paramagnetic
low-spin complex
high-spin complex
only electron configurations d4, d5, d6, or d7 can have low or high spin
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Tetrahedral Geometry and

Crystal Field Splitting
because the ligand approach interacts more

strongly with the planar orbitals in the
tetrahedral geometry, their energies are raised
most high-spin complexes

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Square Planar Geometry and

Crystal Field Splitting
d8 metals
the most complex splitting pattern
most are low-spin complexes

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Applications of
extraction of metals from ores
silver and gold as cyanide complexes
nickel as Ni(CO)4(g)
use of chelating agents in heavy metal poisoning

EDTA for Pb poisoning
chemical analysis
qualitative analysis for metal ions
blue = CoSCN+
red = FeSCN2+
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Applications of
commercial coloring agents
prussian blue = mixture of hexacyanoFe(II) and Fe(III)
inks, blueprinting, cosmetics, paints
biomolecules
porphyrin ring
cytochrome C
hemoglobin
chlorphyll
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chlorophyll
39
Applications of
carbonic anhydrase
catalyzes the reaction between water and CO2
contains tetrahedrally complexed Zn2+

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Applications of
Drugs and Therapeutic Agents
cisplatin
anticancer drug

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Chemistry: A Molecular Approach, 1st Ed.

Some Al3+ ions

Properties and Electron Configuration

and very different tot he properties of the main group metals

in general, the transition metals have two valence

electrons we are filling the d orbitals in the shell

Tro, Chemistry: A Molecular App

Tro, Chemistry: A Molecular App

the transition metals

slightly increases down

Tro, Chemistry: A Molecular App

Tro, Chemistry: A Molecular App

make a neutral compound it is called a coordination

coordination number range from 2 to 12, with the most

Tro, Chemistry: A Molecular App

Tro, Chemistry: A Molecular App

Complex Ion Formation

Tro, Chemistry: A Molecular App

Ligands with Extra Teeth

lone pairs on different atoms that are separate enough

chelate is a complex ion containing a

ligand is called the chelating agent

Tro, Chemistry: A Molecular App

Tro, Chemistry: A Molecular App

Tro, Chemistry: A Molecular App

Complex Ions with Polydentate Ligands

Tro, Chemistry: A Molecular App

Geometries in Complex Ions

Tro, Chemistry: A Molecular App

Naming Coordination Compounds

1) name each ligand alphabetically, adding a prefix in front of

5) write the name of the cation followed by the name of

Tro, Chemistry: A Molecular App

Tro, Chemistry: A Molecular App

Common Metals found in

Tro, Chemistry: A Molecular App

Tro, Chemistry: A Molecular App

Tro, Chemistry: A Molecular App

Ex. 24.5 Draw the structures and label the type

Tro, Chemistry: A Molecular App

Tro, Chemistry: A Molecular App

Ex 24.7 Determine if the cis-trans isomers of

draw the mirror

Bonding in Coordination Compounds

Tro, Chemistry: A Molecular App

Tro, Chemistry: A Molecular App

Bonding in Coordination Compounds

ligand for the charge on the metal cation

Tro, Chemistry: A Molecular App

Splitting of d Orbital Energies due to

Tro, Chemistry: A Molecular App

Strong and Weak Field Splitting

Tro, Chemistry: A Molecular App

Complex Ion Color

Tro, Chemistry: A Molecular App

Complex Ion Color and

Tro, Chemistry: A Molecular App

crystal field strength increases as the charge on

Magnetic Properties and

orbitals depends on the strength of the crystal field

Low Spin & High Spin Complexes

Tetrahedral Geometry and

because the ligand approach interacts more

Tro, Chemistry: A Molecular App