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Coordination Compounds
23-1
The Transition Elements and Their Coordination
Compounds
23-2
Figure 23.1 The transition elements (d block) and inner
transition elements (f block) in the periodic table.
23-3
Properties of the Transition Metals
23-4
Figure 23.2 The Period 4 transition metals.
23-5
Electron Configurations of
Transition Metals and their Ions
The d-block elements have the general condensed
ground-state configuration [noble gas]ns2(n – 1)dx where
n = 4 to 7 and x = 1 to 10.
23-6
Table 23.1 Orbital Occupancy of the Period 4 Transition Metals
PLAN: We locate the element in the periodic table and count its
position in the respective transition series. These elements are
in Periods 4 and 5, so the general electron configuration is
[noble gas]ns2(n – 1)dx. For the ions, we call that ns electrons
are lost first.
SOLUTION:
(a) Zr is the second element in the 4d series:
[Kr]5s24d2
23-8
Sample Problem 23.1
[Kr]4d3
23-9
Trends in the Properties of
Transition Metals
Across a period the following trends are observed:
23-10
Figure 23.3 Trends in key atomic properties of Period 4
elements.
23-11
Trends in the Properties of
Transition Metals
Within a group the trends also differ from those observed
for main group elements.
23-12
Trends in the Properties of
Transition Metals
Electronegativity increases within a group from Period 4
to 5, then generally remains unchanged from Period 5 to
6. The heavier elements often have high EN values.
Although atomic size increases slightly down the group, nuclear
charge increases much more, leading to higher EN values.
23-13
Figure 23.4 Vertical trends in key properties within the
transition elements.
23-14
Oxidation States of Transition Metals
23-15
Figure 23.5 Aqueous oxoanions of transition elements.
+2 +6 +7
Mn2+ MnO4 2−
MnO4−
+5 +6 +7
VO43− Cr2O7
2−
MnO4−
23-16
Table 23.2 Oxidation States and d-Orbital Occupancy of the
Period 4 Transition Metals*
23-17
Metallic Behavior of Transition Metals
23-18
Table 23.3 Standard Electrode Potentials of Period 4 M2+ Ions
Half-Reaction E°(V)
23-19
Color and Magnetic Behavior
23-20
Figure 23.6 Colors of representative compounds of the Period 4
transition metals.
23-21
Table 23.4 Some Properties of Group 6B(6) Elements
23-22
Lanthanides and Actinides
The lanthanides are also called the rare earth elements.
23-23
Sample Problem 23.2 Finding the Number of Unpaired Electrons
SOLUTION:
Sm is the eighth element after Xe. Two electrons go into the 6s
sublevel. In general, the 4f sublevel fills before the 5d, so the
remaining six electrons go into the 4f sublevel.
The condensed configuration of Sm is [Xe]6s24f6.
23-24
Sample Problem 23.2
↑↓ ↑ ↑ ↑ ↑ ↑ ↑
6s 4f 5d 6p
23-25
Coordination Compounds
A coordination compound contains at least one complex
ion, which consists of a central metal cation bonded to
molecules and/or anions called ligands.
The complex ion is associated with counter ions of
opposite charge.
The complex ion [Cr(NH3)6]3+ has a central Cr3+ ion bonded to six
NH3 ligands. The complex ion behaves like a polyatomic ion in
solution.
23-26
Coordination Number
23-27
Figure 23.7 Components of a coordination compound.
23-28
Table 23.5 Coordination Numbers and Shapes of Some
Complex Ions
Coordination
Number Shape Examples
2 Linear [CuCl2]-, [Ag(NH3)2]+, [AuCl2]-
23-30
Table 23.6 Some Common Ligands in Coordination Compounds
23-31
Chelates
EDTA has six donor atoms and forms very stable complexes
with metal ions.
23-32
Formulas of Coordination Compounds
23-33
Determining the Charge of the Metal Ion
There are two neutral NH3 ligands and four Cl- ligands. To have an
overall charge of 2-, the metal ion must have a charge of 2+.
Charge of complex ion = charge of metal ion + total charge of ligands
2- = charge of metal ion + [(2 x 0) + (4 x -1)]
Charge of metal ion = (-2) – (-4) = +2 or 2+
23-34
[Co(NH3)4Cl2]Cl contains a complex cation.
The charge of the cation is balanced by the Cl- counter ion, so the
cation must be [Co(NH3)4Cl2]+.
There are four neutral NH3 ligands and two Cl- ligands. To have an
overall charge of 1+, the metal ion must have a charge of 3+.
Charge of complex ion = charge of metal ion + total charge of ligands
1+ = charge of metal ion + [(4 x 0) + (2 x 1-)]
Charge of metal ion = (+1) – (2-) = +3 or 3+
23-35
Naming Coordination Compounds
• The cation is named before the anion.
• Within the complex ion, the ligands are named in alphabetical order
before the metal ion.
– Anionic ligands drop the –ide and add –o after the root name.
• A numerical prefix is used to indicate the number of ligands of a
particular type.
– Prefixes do not affect the alphabetical order of ligand names.
– Ligands that include a numerical prefix in the name use the
prefixes bis (2), tris (3), or tetrakis (4) to indicate their number.
• A Roman numeral is used to indicate the oxidation state for a metal
that can have more than one state.
• If the complex ion is an anion, we drop the ending of the metal name
and add –ate.
23-36
Table 23.7 Names of Some Neutral and Anionic Ligands
Neutral Anionic
Name Formula Name Formula
Aqua H2O Fluoro F-
Ammine NH3 Chloro Cl-
Carbonyl CO Bromo Br-
Nitrosyl NO Iodo I-
Hydroxo OH-
Cyano CN-
23-37
Table 23.8 Names of Some Metal Ions in Complex Anions
23-38
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
23-39
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+
dichlorobis(ethylenediamine)cobalt(III) nitrate
23-40
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
23-41
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
23-42
Constitutional Isomers of Coordination
Compounds
Compounds with the same formula, but with the atoms
connected differently, are constitutional isomers.
23-43
Figure 23.8 A pair of linkage (constitutional) isomers
The nitrite ion can bind either through the N atom or either one of
the O atoms.
23-44
Ligands that have more than one donor atom
23-45
Stereoisomers of Coordination
Compounds
Stereoisomers are compounds that have the same atomic
connections but different spatial arrangements of their
atoms.
Geometric or cis-trans isomers occur when atoms or
groups can either be arranged on the same side or on
opposite sides of the compound relative to the central
metal ion.
23-46
Figure 23.9A Geometric (cis-trans) isomerism.
In the cis isomer, identical ligands are adjacent to each other, while in
the trans isomer they are across from each other.
23-47
Figure 23.9B Geometric (cis-trans) isomerism.
23-48
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]+.
23-49
Figure 23.10B Optical isomerism in an octahedral complex ion.
23-50
Figure 23.11 Important types of isomerism in coordination
compounds.
23-51
Sample Problem 23.4 Determining the Type of Stereoisomerism
PROBLEM: Draw stereoisomers for each of the following and state the
type of isomerism:
(a) [Pt(NH3)2Br2] (square planar) (b) [Cr(en)3]3+ (en = H2NCH2CH2NH2)
PLAN: We determine the geometry around each metal ion and the
nature of the ligands. If there are different ligands that can be
placed in different positions relative to each other, geometric
(cis-trans) isomerism occurs. Then we see whether the mirror
image of an isomer is superimposable on the original. If it is
not, optical isomerism also occurs.
23-52
Sample Problem 23.4
SOLUTION:
(a) The square planar Pt(II) complex has two different types of
monodentate ligands. Each pair of ligands can be next to
each other or across from each other. Thus geometric
isomerism occurs.
23-53
Sample Problem 23.4
23-54
Bonding in Complex Ions
23-55
Figure 23.12 Hybrid orbitals and bonding in the octahedral
[Cr(NH3)6]3+ ion.
23-56
Figure 23.13 Hybrid orbitals and bonding in the square planar
[Ni(CN)4]2- ion.
23-57
Figure 23.14 Hybrid orbitals and bonding in the tetrahedral
[Zn(OH)4]2- ion.
23-58
Figure 23.15 An artist’s wheel.
23-59
Table 23.9 Relation Between Absorbed and Observed Colors
23-60
Crystal Field Theory
23-61
Figure 23.16 The five d-orbitals in an octahedral field of ligands.
23-62
Figure 23.17 Splitting of d-orbital energies in an octahedral
field of ligands.
23-63
Figure 23.18 The effect of ligands and splitting energy on
orbital occupancy.
23-64
Figure 23.19 The color of [Ti(H2O)6]3+.
23-65
Figure 23.19 The color of [Ti(H2O)6]3+.
When the ion absorbs light, electrons can move from the lower t2g
energy level to the higher eg level. The difference in energy
between the levels (Δ) determines the wavelengths of light
absorbed. The visible color is given by the combination of the
wavelengths transmitted.
23-66
The Colors of Transition Metal Complexes
23-67
Figure 23.20 Effects of oxidation state and ligand on color.
23-68
Figure 23.21 The spectrochemical series.
I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO
SMALLER LARGER
LONGER SHORTER
23-69
Sample Problem 23.5 Ranking Crystal Field Splitting Energies (Δ)
for Complex Ions of a Metal
SOLUTION: The ligand field strength is CN- > NH3 > H2O, so the
relative size of Δ and energy of light absorbed will be
23-70
The Magnetic Properties of Transition
Metal Complexes
Magnetic properties are determined by the number of
unpaired electrons in the d orbitals of the metal ion.
Hund’s rule states that e- occupy orbitals of equal energy
one at a time. When all lower energy orbitals are half-
filled:
- The next e- can enter a half-filled orbital and pair up by
overcoming a repulsive pairing energy, (Epairing).
- The next e- can enter an empty, higher, energy orbital by
overcoming Δ.
23-71
Figure 23.22 High-spin and low-spin octahedral complex
ions of Mn2+.
23-72
Figure 23.23 Orbital occupancy for high-spin and low-spin
octahedral complexes of d4 through d7 metal ions.
23-73
Sample Problem 23.6 Identifying High-Spin or Low-Spin Complex
Ions
PROBLEM: Iron (II) forms a complex in hemoglobin. For each of the
two octahedral complex ions [Fe(H2O)6]2+ and [Fe(CN)6]4,
draw an energy diagram showing orbital splitting, predict
the number of unpaired electrons, and identify the ion as
low spin or high spin.
23-74
Sample Problem 23.6
SOLUTION:
eg
Potential energy
↑ ↑ eg
Potential energy
↑↓ ↑ ↑ t2g
↑↓ ↑↓ ↑↓ t2g
[Fe(H2O)6]2+ [Fe(CN)6]4-
high-spin low-spin
23-75
Figure 23.24A Splitting of d-orbital energies by a tetrahedral
field of ligands.
23-76
Figure 23.24B Splitting of d-orbital energies by a square planar
field of ligands.
23-77
Chemical Connections
Figure B23.1 Hemoglobin and the octahedral complex in heme.
23-78
Table B23.1 Some Transition Metal Trace Elements in Humans
23-79
Chemical Connections
Figure B23.2 The tetrahedral Zn2+ complex in carbonic anhydrase.
23-80