Chapter 20.

Transition Metals and Coordination

Chemistry

20.1 The Transition Metals: A Vanadium metal (center) and in solution as

Survey V2+(aq), V3+(aq), VO2+(aq), and VO2+(aq),
20.2 The First-Row Transition (left to right).
Metals
20.3 Coordination Compounds
20.4 Isomerism
20.5 Bonding in Complex Ions:
The Localized Electron Model
20.6 The Crystal Field Model
20.7 The Molecular Orbital Model
20.8 The Biological Importance of
Coordination Complexes

Figure 20.1: Transition elements on the periodic

table
 20.5 Bonding in Complex Ions: The Localized Electron Model

¾ Recall formation of hybrid orbitals for bonding in molecules (chapt. 14).

¾ Formation of coordinate covalent bonds between a metal ion and a ligand (L) is
through a Lewis acid-base interaction.
M L = M L

empty metal ion hybrid lone pair on the ligand in

atomic orbital a hybrid atomic orbital

Figure 20.19: Set of six d2sp3

hybrid orbitals on Co3+.

Co3+ is d2sp3 hybridized in the

complex ion Co(NH3)63+

Figure 20.20: Hybrid orbitals required

for tetrahedral, square planar, and linear complex ions.

• Co2+ is sp3 hybridized in tetrahedral CoCl42-

complex ion.
• Ni2+ is dsp2 hybridized in the square planar
Ni(CN)42- complex ion.
• Ag+ is sp hybridized in the linear Ag(NH3)2+
ion.
 Bonding in Complex metal ions

• Limitations of the LE Model of Bonding in complex metal ions:

1. The VSEPR model for predicting structure does not work

for complex ions.

2. The LE model cannot predict the properties of the metal

complex ion, e.g. magnetism and color.

• Magnetic properties and colors

– the crystal field model based on d-orbital splitting

20.6 The Crystal Field Model

• Accounts for the color and magnetic properties of complex ions
• Key assumptions:
1. ligands are approximated by negative point charges.
2. metal – ligand bonding is entirely ionic.
Octahedral Complexes
(See Figure 20.21)
• Orientation of the 3d orbitals relative to the point-charge ligands leads to
splitting of the 3d orbital energies (Δ)
• t2g set of orbitals (dxz, dyz, dxy) – lower in energy
• eg set of orbitals (dz2 , dx2-y2 ) – higher in energy

E E
eg
large eg small
Δ Δ
t2g t2g
Strong-field case Weak-field case
Figure 20.21: Octahedral arrangement of point-charge
ligands and the orientation of the 3d orbitals.

Figure 20.22: Energies of the 3d orbitals

for a metal ion in an octahedral complex.
 Figure 20.23: possible electron arrangements in the split 3d orbitals of an
octahedral complex of Co3+

• In a strong-field case (i.e. large Δ), the electrons of the metal ion pair in
the lower-energy t2g orbitals.
• In a weak-field case (i.e. small Δ), the electrons will occupy all five
orbitals before pairing occurs.

Example 20.4
Fe(CN)63- experimentally known to have one unpaired electron. Does the
CN- ligand produce a strong or weak field?
Fe3+ has 3d5 electron configuration e g

eg large
small
Δ
t2g Δ t2g
weak-field (high-spin) case strong-field (low-spin) case
• CN- is a strong-field ligand toward the Fe3+ ion.

• Spectrochemical series of ligands:

CN- > NO2- > en > NH3 > H2O > OH- > F- > Cl- > Br- > I-
strong-field ligands weak-field ligands
(large Δ) (small Δ)
decreasing Δ values for a given metal ion
 • The magnitude of Δ for a given ligand increases as the charge on the metal
ion increases.

Example
Account for the magnetic properties of Co(NH3)63+ and CoF63-
Co3+ with 3d5 electron configuration in both cases.
eg
large eg low
Δ Δ
t2g t2g
Co(NH3)6 3+ CoF 6
3-

diamagnetic paramagnetic
experimentally observed.
¾ Origin of Color in Complex metal ions
• The same d orbital energy splitting explains the colors of complex ions.
E
eg
ΔE = hc/λ= 1240 (eV)/ λ(nm)
t2g if λ = wavelength of light absorbed is in the visible

• The visible spectrum (Figure 20.24)

400 700 nm
Octahedral complexes of Cr3+
ΔE = 3.1 eV 1.8 eV 3d3
If ΔE < 1.8 eV, the wavelength of the E
light absorbed will be in the infrared and eg
not visible.
Δ
t2g
 Figure 20.24: Visible spectrum

Figure 20.26: The complex ion Ti(H2O)63+ absorbs light and

becomes excited.
 Complexes with Other Coordination Geometries
– Octahedral complexes (already considered)
– Tetrahedral complexes
– Square planar complexes
– Linear complexes

E For a given ligand and metal ion:

t2g
Δtet = 4/9 Δoct
dxy dxz dyz
Δ
eg
d z2 dz2-y2

all tetrahedral complexes produce the weak-field case.

e.g. CoCl42-, 3d7 (Example 20.6)

For the crystal field diagrams of square planar and linear complexes
See Figure 20.29

Figure 20.27: Tetrahedral and octahedral arrangements of

ligands shown inscribed in cubes.
 Figure 20.28: Crystal field diagrams for octahedral and
tetrahedral complexes

Figure 20.29: Crystal field diagram for a square planar complex oriented
in the xy plane (b) crystal field diagram for a linear complex
 Complex metal ions
• Bonding in complex metal ions
– the localized electron model is used but it has major limitations:
1. The VSEPR model for predicting structure does not work well for
complex ions.
2. The LE model cannot predict the properties of the metal complex
ion, e.g. magnetism and color.
• Magnetic properties and colors
– the crystal field model based on d-orbital splitting
¾The Molecular Orbital Model of Complex Metal Ions
Figure 20.30
•Consider the general octahedral complex with formula ML6n+.
– dz2 and dx2-y2 orbitals point at the ligands and thus will
form MOs with the ligand lone pair orbitals
• the σMOs in the complex ion involve dz2 , dx2-y2 , 4s, 4px,
4py, and 4pz orbitals
– dxy, dxz, and dyz orbitals are not involved in σ bonding
with the ligands

Figure 20.31: The MO energy- ML6n+

level diagram for an octahedral
complex ion (ML6n+).

• the dxz, dyz and dxy orbitals ( the t2g set) of

the metal ion remain unchanged in the
complex ion since they do not overlap
with the ligand orbitals
– they are nonbonding orbitals.
• the eg* MOs are antibonding orbitals
(since they are higher in energy than the
atomic orbitals that mix to form them)
– the eg* MOs are composed of dz2 and
dx2-y2 atomic orbitals primarily (little
or no mixing with ligand atomic
orbitals due to the large energy
difference btw them)
• the MO model has the same d orbital
splitting as the crystal field model.
 Figure 20.32: MO energy-level diagram for CoF63-, which yields
the high-spin (a) whereas Co(NH3)63+ yields low-spin (b).

¾ the MO model accounts for the magnetic and spectral properties of

complex ions (just like the crystal field model).
• the MO model is a more realistic description of the metal-ligand bonding in
complex ions.

20.8 The Biological Importance of Coordination Complexes

of Metal Ions
• In biological systems, metal ion complexes find diverse applications
– transport and storage of oxygen and other essential elements
– electron transfer agents
– catalysts (enzymes)
– drugs
– etc.
Figure 20.33: The heme
complex in which an Fe2+ ion
is coordinated to four
nitrogen atoms of a planar
porphyrin ligand.

Figure 20.34: Chlorophyll is a porphyrin complex of Mg2+,

essential to photosynthesis.
 Figure 20.35: Representation of the myoglobin molecule

Figure 20.36: Representation of the hemoglobin structure.

Each hemoglobin stores 4 oxygen (O2) molecules.