LANTHANIDES AND ACTINIDES AND

HEAVY TRANSITION METALS

CHEM 252
N.O. BOADI

1
 OUTLINE
• 2nd and 3rd row transition metals
• Lanthanides
• Actinides

2
 Assessment
• First quiz after 2nd and 3rd row transition
metals
– Mode: theory
• Mid-semester exams focused on lanthanides
– Mode: theory
• End of semester covers all topics taught
– Mode: Multiple choice

3
 Reading material
• S.A. Cotton, Lanthanides and Actinides, Macmillan,
London, 1991 pp. 191
• J.J. Katz, G.T. Seaborg & L.R. Morss, The Chemistry of
the Actinides, 2nd ed., Chapman & Hall, London, 1986
(a major reference work, see especially Ch. 14
Summary & Comparative Aspects)
• J.E. Huheey, E.A. & R.L. Keiter, Inorganic Chemistry, 4th
ed., HarperCollins, N.Y., 1993 p. 599-617
• F.A. Cotton & G. Wilkinson, Advanced Inorganic
Chemistry, 5th ed., Wiley, N.Y., 1988 Ch. 20, 21

4
Electronic Structure and Reactivity of
the Transition Metals
• As we go across the first-row transition metals
from left to right, electrons are added to the
3d subshell to neutralize the increase in the
positive charge of the nucleus as the atomic
number increases.
• With two important exceptions, the
3d subshell is filled as expected based on the
aufbau principle and Hund’s rule.

5
Electronic Structure and Reactivity of
the Transition Metals
• however, chromium has a 4s13d5 electron
configuration rather than the
4s23d4 configuration predicted by the aufbau
principle, and copper is 4s13d10 rather than
4s23d9.
• These anomalies may be attributed to the
extra stability associated with half-filled
subshells.

6
Electronic Structure and Reactivity of
the Transition Metals
• Because the ns and (n − 1)d subshells in these
elements are similar in energy, even relatively
small effects are enough to produce apparently
anomalous electron configurations.

Sc Ti V Cr Mn Fe Co Ni Cu Zn

4s23d1 4s23d2 4s23d3 4s13d5 4s23d5 4s23d6 4s23d7 4s23d8 4s13d10 4s23d10

7
Electronic Structure and Reactivity of
the Transition Metals
• In the second-row transition metals, electron–
electron repulsions within the 4d subshell
cause additional irregularities in electron
configurations that are not easily predicted.
• For example, Nb and Tc, with atomic numbers
41 and 43
– both have a half-filled 5s subshell, with 5s14d4 and
5s14d6 valence electron configurations,
respectively
8
Electronic Structure and Reactivity of
the Transition Metals
• Further complications occur among the third-
row transition metals, in which the 4f, 5d, and
6s orbitals are extremely close in energy.

2nd Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Row
3rd La Hf Ta W Re Os Ir Pt Au Hg
Row

9
Electronic Structure and Reactivity of
the Transition Metals
• The atomic radii of the elements in the 5d
series (Hf, Ta, W….) are not much bigger than
those of their 4d series congeners (Zr, Nb, Mo,
….).
• In fact, the atomic radius of Hf is smaller than
that of Zr even though it appears in a later
period.
• To understand this anomaly, we need to
consider the effect of the lanthanides.

10
 LANTHANIDE CONTRACTION
• The atomic radii of the members of Group 3
(Sc, Y, La) increase down the group, as
expected from the increase in principal
quantum number of the outermost electrons.
• However, the 14 lanthanides intervene
between La and Hf, with the corresponding
additional electrons occupying the poorly
shielding 4f orbitals.

11
 LANTHANIDE CONTRACTION
• Because the atomic number has increased by
32 between Zr and Hf without a
corresponding increase in shielding, the
overall effect is that the atomic radii of the 5d-
series elements are much smaller than
expected.
• This reduction in radius is the effect of
lanthanide contraction.

12
 LANTHANIDE CONTRACTION
• The lanthanide contraction also affects the
ionization energies of the 5d-series elements,
making them higher than expected.
• Some of the metals-specifically Au, Pt, Ir, and
Os have much high ionization energies that
they are unreactive under normal conditions.

13
 OXIDATION STATES
• The group oxidation number of an element is its
group (in the 1-18 notation).
• The corresponding oxidation state can be
achieved by elements that lie towards the left of
the d block but not by elements on the right.
– For example, Scandium, yttrium, and lanthanum in
group3, with configurations nd1(n+1)S2, are found in
aqueous solution only in oxidation state +3, which
corresponds to the loss of all outermost electrons, and
the majority of the complexes contain the elements in
this state.

14
 OXIDATION STATES
• The group oxidation state is never achieved
after Group 8 (Fe, Ru, and Os).
• This limit on the maximum oxidation state
correlates with increase in ionization energy
and hence, noble character from left to right
across each series in the d-block.

15
 OXIDATION STATES
• Most +1 d-metal cations (M+) disproportionate
(to M and M2+) because the bonds in the solid
metal are so strong, and for the 3d metals, the
+2 oxidation state is in combination with hard
ligands.
• Exceptions are mainly confined to metal-metal
bonded and organometallic compounds, such
as the metal carbonyls Ni (CO)4 and Mo(CO)6
in which the metal is in the zero oxidation
state.
16
 OXIDATION STATES
• The dipositive aqua ions, M2+(aq) (specifically,
the octahedral complexes [M(OH2)6]2+), play
an important role in the chemistry of the 3d-
series metals.
• Many of these ions are coloured as a result of
d-d transitions in the visible region of the
spectrum.
– For example, Cr2+(aq) is blue, Fe2+ (aq) is green,
Co2+ (aq) is pink, Ni2+(aq) is green, and Cu2+(aq) is
blue.
17
 OXIDATION STATES
• The +3 oxidation state is common at the left of
the period, and is the only oxidation state
normally encountered for scandium.
• Ti, V, and Cr all form a wide range of compounds
in the oxidation state +3.
• In line with increasing ionization energy, the
stability of M(III) decreases across the period.
• Mn(II) is especially stable due to its half-filled d
shell, and relatively few Mn(III) compounds are
known.
18