Lecture PowerPoint

Chemistry
The Molecular Nature of
Matter and Change
Fifth Edition

Martin S. Silberberg

23-1 Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Chapter 23

The Transition Elements and Their

Coordination Compounds

23-2
 The Transition Elements and Their Coordination Compounds

23.1 Properties of the Transition Elements

23.2 The Inner Transition Elements

23.3 Highlights of Selected Transition Metals

23.4 Coordination Compounds

23.5 Theoretical Basis for the Bonding and Properties of Complexes

23-3
 Figure 23.1 The transition elements (d block) and inner transition
elements (f block) in the periodic table.

23-4
 Figure 23.2 The Period 4 transition metals.

23-5
23-6
 Sample Problem 23.1 Writing Electron Configurations of Transition
Metal Atoms and Ions

PROBLEM: Write condensed electron configurations for the following: (a) Zr;
(b) V3+; (c) Mo3+. (Assume that elements in higher periods
behave like those in Period 4.)
PLAN: The general configuration is [noble gas] ns2(n - 1)dx. Recall that in
ions the ns electrons are lost first.

SOLUTION:
(a) Zr is the second element in the 4d series: [Kr]5s24d2.
(b) V is the third element in the 3d series: [Ar]4s23d3. In forming V3+,
three electrons are lost (two 4s and one 3d), so V3+ is a d2 ion: [Ar]3d2.
(c) Mo lies below Cr in Group 6B(6), so we expect the same exception
configuration as for Cr. Thus, Mo is [Kr]5s14d5. In forming the ion, Mo3+
loses the one 5s and two of the 4d electrons to become a 4d3 ion: [Kr]4d3.

23-7
 Figure 23.3 Horizontal trends in key atomic properties of the
Period 4 elements.

23-8
 Figure 23.4
Vertical trends in key properties within the transition elements.

23-9
 Figure 23.5 Aqueous oxoanions of transition elements.

One of the most characteristic

chemical properties of these
elements is the occurrence of
multiple oxidation states.

Mn2+ MnO42− MnO4−

MnO4−
Cr2O72−
VO43−

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23-11
23-12
 Figure 23.6

Colors of representative compounds of the Period 4 transition

metals. sodium chromate nickel(II) nitrate
hexahydrate
potassium zinc sulfate
Titanium(IV) oxide
ferricyanide heptahydrate

scandium oxide manganese(II) copper(II)

chloride sulfate
vanadyl sulfate tetrahydrate cobalt(II) pentahydrate
dihydrate chloride
hexahydrate

23-13
23-14
 Sample Problem 23.2 Finding the Number of Unpaired Electrons

PROBLEM: The alloy SmCo5 forms a permanent magnet because both

samarium and cobalt have unpaired electrons. How many
unpaired electrons are in the Sm atom (Z = 62)?

PLAN: Write the condensed configuration of Sm and, using Hund’s

rule and the aufbau principle, place electrons into a partial
orbital diagram.

SOLUTION: Sm is the eighth element after Xe. Two electrons go into the 6s
sublevel and the remaining six electrons into the 4f (which fills
before the 5d).
Sm is [Xe]6s24f6

6s 4f 5d

There are 6 unpaired e− in Sm.

23-15
 Figure 23.7 The bright colors of chromium (VI) compounds.

23-16
23-17
 Figure 23.8 Steps in producing a black-and-white negative.

23-18
 Figure 23.9 Components of a coordination compound.

models wedge diagrams chemical formulas

23-19
 Structures of Complex Ions:
Coordination Numbers, Geometries, and Ligands

•Coordination number - the number of ligand atoms that are bonded

directly to the central metal ion. The coordination number is specific for
a given metal ion in a particular oxidation state and compound.

•Geometry - the geometry (shape) of a complex ion depends on the

coordination number and nature of the metal ion.

•Donor atoms per ligand - molecules and/or anions with one or more
donor atoms that each donate a lone pair of electrons to the metal ion to
form a covalent bond.

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23-22
23-23
 Formulas of Coordination Compounds

Rules for writing formulas:

1. The cation is written before the anion.

2. The charge of the cation(s) is balanced by the charge

of the anion(s).

3. In the complex ion, neutral ligands are written before

anionic ligands, and the formula for the whole ion is
placed in brackets.

23-24
 Names of Coordination Compounds

Rules for naming complexes:

1. The cation is named before the anion.

2. Within the complex ion, the ligands are named, in alphabetical
order, before the metal ion.
3. Neutral ligands generally have the molecule name, but there are a
few exceptions. Anionic ligands drop the -ide and add -o after the
root name.
4. A numerical prefix indicates the number of ligands of a particular
type.
5. The oxidation state of the central metal ion is given by a Roman
numeral (in parentheses) only if the metal ion can have more than
one state, as in the compound named in rule 1.
6. If the complex ion is an anion we drop the ending of the metal
name and add -ate.

23-25
 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 systematic name of [Co(en)2Cl2]NO3?
(c) What is the formula of tetraaminebromochloroplatinum(IV)
chloride?
(d) What is the formula of hexaaminecobalt(III) tetrachloro-
ferrate(III)?
PLAN: Use the rules presented - Formulas and Names .

SOLUTION: (a) The complex ion is [AlF6]3-.

Six (hexa-) fluorines (fluoro-) are the ligands - hexafluoro
Aluminum is the central metal atom - aluminate

Aluminum has only the +3 ion so we don’t need Roman

numerals.

sodium hexafluoroaluminate

23-26
 Sample Problem 23.3 Writing Names and Formulas of Coordination
Compounds

(b) There are two ligands, chlorine and ethylenediamine -

dichloro, bis(ethylenediamine)
The complex ion is the cation and we have to use Roman numerals
for the cobalt oxidation state since it has more than one - (III)
The anion, nitrate, is named last.
dichlorobis(ethylenediamine)cobalt(III) nitrate

(c) 4 NH3 Br- Cl- Pt4+ Cl-

tetraamminebromochloroplatinum(IV) chloride
[Pt(NH3)4BrCl]Cl2
(d) 6 NH3 Co3+ 4 Cl- Fe3+
hexaamminecobalt(III) tetrachloro-ferrate(III)

[Co(NH3)6][Cl4Fe]3

23-27
23-28
 Figure 23.10
Important types of isomerism in coordination compounds.

ISOMERS
Same chemical formula, but different properties

Constitutional (structural) isomers Stereoisomers

Atoms connected differently Different spatial arrangement

Coordination
Coordination Linkage
Linkage Geometric
Geometric (cis-
(cis- Optical
Optical isomers
isomers
isomers
isomers isomers
isomers trans)
trans) isomers
isomers (enantiomers)
(enantiomers)
(diastereomers)
(diastereomers)
Ligand
Ligand and
and Different
Different donor
donor Nonsuperimposable
Nonsuperimposable
counter-ion
counter-ion atom
atom Different
Different mirror
mirror images
images
exchange
exchange arrangement
arrangement
around
around metal
metal ion
ion

23-29
 Linkage isomers

23-30
 Figure 23.11 Geometric (cis-trans) isomerism.

23-31
 Figure 23.12

Optical isomerism in an
octahedral complex ion.

23-32
 Sample Problem 23.4 Determining the Type of Stereoisomerism

PROBLEM: Draw all stereoisomers for each of the following and state the type
of isomerism:
(a) [Pt(NH3)2Br2] (b) [Cr(en)3]3+ (en = H2NCH2CH2NH2)

PLAN: Determine the geometry around each metal ion and the nature of
the ligands. Place the ligands in as many different positions as
possible. Look for cis-trans and optical isomers.

SOLUTION: (a) Pt(II) forms a square planar complex and there are two pairs
of monodentate ligands - NH3 and Br.
Br NH3 H3N Br These are geometric isomers;
Pt Pt they are not optical isomers
H3 N Br since they are superimposable
H3N Br
on their mirror images.
trans cis

23-33
 Sample Problem 23.4 Determining the Type of Stereoisomerism

(b) Ethylenediamine is a bidentate ligand. Cr3+ is hexacoordinated and

will form an octahedral geometry.
Since all of the ligands are identical, there will be no geometric isomerism
possible.
3+ 3+
N N
The mirror images are
N N N N nonsuperimposable
Cr Cr and are therefore
N N N N optical isomers.
N N

rotate 3+
N
N N
Cr
N N
N
23-34
 Figure 23.13
Hybrid orbitals and bonding in the octahedral [Cr(NH3)6]3+ ion.

23-35
 Figure 23.14

Hybrid orbitals and bonding in the square planar [Ni(CN)4]2- ion.

23-36
 Figure 23.15
Hybrid orbitals and bonding in the tetrahedral [Zn(OH)4]2- ion.

23-37
 Figure 23.16 An artist’s wheel.

23-38
23-39
 Figure 23.17 The five d-orbitals in an octahedral field of ligands.

23-40
 Figure 23.18 Splitting of d-orbital energies by an octahedral field
of ligands.

 is the splitting energy

23-41
 Figure 23.19 The effect of the ligand on splitting energy.

23-42
 Figure 23.20 The color of [Ti(H2O)6]3+.

23-43
 Figure 23.21 Effects of the metal oxidation state and of ligand
identity on color.

[V(H2O)6]2+ [V(H2O)6]3+

[Cr(NH3)6]3+ [Cr(NH3)5Cl ]2+

23-44
 Figure 23.22 The spectrochemical series.

•For a given ligand, the color depends on the oxidation state of the metal ion.

•For a given metal ion, the color depends on the ligand.

I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO

WEAKER FIELD STRONGER FIELD

SMALLER  LARGER 

LONGER  SHORTER 

23-45
 Sample Problem 23.5 Ranking Crystal Field Splitting Energies for
Complex Ions of a Given Metal

PROBLEM: Rank the ions [Ti(H2O)6]3+, [Ti(NH3)6]3+, and [Ti(CN)6]3- in terms of

the relative value of  and of the energy of visible light absorbed.
PLAN: The oxidation state of Ti is 3+ in all of the complexes so we are
looking at the crystal field strength of the ligands. The stronger the
ligand the greater the splitting and the higher the energy of the light
absorbed.

SOLUTION: The field strength according to is CN- > NH3 > H2O. So
the relative values of  and energy of light absorbed will be

[Ti(CN)6]3- > [Ti(NH3)6]3+ > [Ti(H2O)6]3+

23-46
 Figure 23.23 High-spin and low-spin complex ions of Mn2+.

23-47
 Figure 23.24 Orbital occupancy for high-spin and low-spin
complexes of d4 through d7 metal ions.

high spin: low spin: high spin: low spin:

weak-field strong-field weak-field strong-field
ligand ligand ligand ligand

23-48
 Sample Problem 23.6 Identifying Complex Ions as High Spin or Low Spin

PROBLEM: Iron (II) forms an essential complex in hemoglobin. For each of the
two octahedral complex ions [Fe(H2O)6]2+ and [Fe(CN)6]4-, draw an
orbital splitting diagram, predict the number of unpaired electrons,
and identify the ion as low or high spin.
PLAN: The electron configuration of Fe2+ gives us information that the iron
has 6d electrons. The two ligands have field strengths shown in
Figure 23.22 .
Draw the orbital box diagrams, splitting the d orbitals into eg and
t2g. Add the electrons noting that a weak-field ligand gives the
maximum number of unpaired electrons and a high-spin complex
and vice-versa. [Fe(CN) ] 4-
6
SOLUTION: [Fe(H2O)6]2+
potential energy

4 unpaired e-- eg
(high spin)
eg no unpaired e--
(low spin)
t2g
t2g
23-49
 Figure 23.25 Splitting of d-orbital energies by a
tetrahedral field of ligands.

tetrahedral

23-50
 Figure 23.26 Splitting of d-orbital energies by a square planar field
of ligands.

23-51
 Figure B23.1 Hemoglobin and the octahedral complex in heme.

23-52
23-53
 Figure B23.2 The tetrahedral Zn2+ complex in carbonic anhydrase.

23-54