Dr S.J.

Heyes

Lanthanides &
Actinides

Textbook version by Nikolaos A. Parisis

Lanthanides & Actinides

Dr S.J. Heyes
Four Lectures in the 2ndYear Inorganic Chemistry Course
Hilary Term 1998

If you have any comments please contact stephen.heyes@chem.ox.ac.uk

Introduction
1 Some Definitions and Viewpoints
2 Occurrence and History of the Elements
3 Nature of f-electrons
4 Electronic Properties
5 Periodicity in the f-Block

Lanthanides
1 Abundance & Distribution
2 Extraction
3 Separation
4 The Metals
5 Examination of the predominance of the 3+ Oxidation State
6 General Features of Lanthanide Chemistry

7 Solution Chemistry

Hydrated Ions
Coordination Compounds
Redox Chemistry - Oxidation States other than +3

8 Magnetism

Paramagnetism
Ferro- and Ferri-Magnetism

9 Electronic Spectroscopy

Luminescence
Phosphors
Bioinorganic Chemistry
Lasers
Solids
~ Includes: Structures, Magnetism, Spectroscopy, Electronic &
Optical Properties, Technological Importance

10 Halides

LnX3
LnX2
SmI2 ~ a versatile organic reagent
Lower Halides

11 Hydrides

LnH2
Hydrogen Storage

12 Oxides
13 Borides
14 Carbides

15 Organometallic Chemistry

Cyclopentadienides
Cyclooctatetraenides
Arenes
Mixed Alkyl Cyclopentadienides

16 Comparisons/Contrasts

Is Y a rare earth?
Should Sc be considered with the Lanthanides, Transition Metals or
as Main Group 3?
Contrasts between Lanthanides & Transition Metals
Similarities between Lanthanides & Other Elements

Actinides
1 Periodicity
2 Occurrence
3 Synthesis of Trans-Uranium Elements
4 Uses of Trans-Uranium Elements
5 The Metals
6 General Observations on Actinides
Including Comparisons with Lanthanides & Transition Metals

7 Oxidation States
8 Aqueous Chemistry
9 Coordination Stereochemistries

10 Uranium Chemistry

Halides
Hydrides
Oxides
Aqueous Chemistry
o

especially the uranyl ion

11 Nuclear Technology
12 Organometallics
13 Super-Heavy Elements?

Problems Set

BIBLIOGRAPHY
Standard Textbook Accounts of increasing degree of sophistication:
J.E. Huheey, E.A. & R.L. Keiter, Inorganic Chemistry, 4th ed., HarperCollins, N.Y.,
1993 p. 599-617
A.G. Sharpe, Inorganic Chemistry, 3rd ed., Longmans, London, 1992 Ch. 1, 26, 27
N.N. Greenwood & A. Earnshaw, Chemistry of the Elements, 2nd ed., ButterworthHeinman, London, 1997 Ch. 30, 31
F.A. Cotton & G. Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley, N.Y.,
1988 Ch. 20, 21
C.S.G. Phillips & R.J.P. Williams, Inorganic Chemistry, OUP, Oxford, 1966 Vol. 2,
Ch. 21, 22

Books on lanthanides and actinides

S.A. Cotton, Lanthanides and Actinides, Macmillan, London, 1991 pp. 191
Open University, The Chemistry of the Lanthanides and the Transactinium Elements,
Open University Press, Milton Keynes, 1977 S304 (The Nature of Chemistry) Unit 27
pp. 61
G.T. Seaborg & W.D. Loveland, The Elements beyond Uranium, Wiley, N.Y., 1990
(An enjoyable account of trans-uranium elements by the discoverer of many)
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)

Books with useful sections

D.A. Johnson, Some Thermodynamic Aspects of Inorganic Chemistry, 2nd ed., CUP,
Cambridge, 1982 p. 158-193 (a very good account of the thermodynamic
underpinning of lanthanide/actinide chemistry)
S.F.A. Kettle, Physical Inorganic Chemistry, Freeman, N.Y., 1996, Ch 11. (fElectron Systems)
R.D. Cowan, Theory of Atomic Structure & Spectra, UCP, Berkley, 1981 p. 598-613
(Lanthanide/Actinide Configurations)
J.A. Cowan, Inorganic Biochemistry, VCH, Weinheim, 1993 p. 300-307 (Ln3+
probes in biology)
C. Elschenbroich & A. Salzer, Organometallics, a Concise Introduction, 2nd ed.,
VCH, Weinheim, 1992 p. 363-5 (Uranocene) p. 442-445 (organolanthanides)
T. Imamoto, Lanthanides in Organic Synthesis, Academic Press, London, 1994 parts
of Ch. 4, 5, 6
P.A. Cox, The Electronic Structure and Chemistry of Solids, OUP, 1987, p.137-145
(Lanthanides)
A.R. West, Solid State Chemistry, Wiley, London, 1984 Ch. 16 (Magnetism), Ch 17.
(Optical Properties)
K. Kosuge, Chemistry of Non-Stoichiometric Compounds, OUP, 1994 p. 219-230
(Hydrogen-absorption)

Article of Interest
W.B. Jensen, The Positions of Lanthanum(Actinium) and Lutetium(Lawrencium) in
the Periodic Table, Journal of Chemical Education, 1982, 59, p. 634-636

Terminology
Definitions?
Rare Earths
La-Lu and Y & Sc occur together in minerals ~ hard to separate from each
other
{Th which occurs in many rare earth minerals is sometimes included in the
definition}
Lanthanides
Usually taken to indicate the 15 elements from La-Lu or the 14 from Ce-Lu
Actinides
The 15 elements from Ac-Lw or the 14 from Th-Lw

Mnemonics:
Lanthanides

Special Feature - The ICL's 1998 Mnemonic

Competition Winner
by Fergus Baillie, Peter Jelfs & Matthew Powell

Lanthanide Chemistry Presents No Problems Since

Everyone Goes To Doctor Heyes's Excrutiatingly
Thorough Yearly Lectures
9

Actinides

Some Viewpoints
"Lanthanum has only one important oxidation state in aqueous
solution, the +3 state. With few exceptions, this tells the whole boring
story about the other 14 Lanthanides"
G.C. Pimentel & R.D. Sprately,
"Understanding Chemistry",
Holden-Day, 1971, p. 862

"These elements (rare earths) perplex us in our researches, baffle us in

our speculations and haunt us in our dreams. They stretch like an
unknown sea before us - mocking, mystifying and murmuring strange
revelations and possibilities"
Sir William Crookes
Address to the British Association, 1887

Due to the increasing technological importance of the rare earths William

Crookes's view seems to be returning to fashion!

10

Where/how do rare earths/actinides fit

into the PERIODIC TABLE?
1751
Swedish Mineralogist A.F. Cronstedt discovers a new heavy mineral

1789
Klaproth shows pitchblende contains a new element, uranium

isolated as a metal in 1841 by Peligot

1794
J. Gadolin isolates "yttria",

but thought it was the pure oxide of Y

1794-1907
ca. 100 claims of elements in the rare earth group, due to:-

problems of separation (very similar properties)

lack of conclusive tests as to whether a mixture was involved

11

pre-1905
Mendeleevian Periodic table could only accommodate 1 element for this
group, La

at one stage W. Crookes thought that apparently different

rare earths were "simply different modifications of the same
element."

Alfred Werner produced a Periodic table in 1905 of

essentially current form, (though he did put spaces for 15
elements between La & Hf - there was no viable atomic theory
at that time!)

1913
X-ray spectroscopy

W. Moseley shows from characteristic X-ray patterns

conclusively that there are only 14 elements between La & Hf

1918-1921
Bohr interprets this as expansion of 4th quantum group from 18 to 32 e-

Lanthanides are therefore identified as the first f-series

1939-45
Lanthanides recognised in fission products of uranium

Techniques to obtain lanthanide separation greatly improved

pre-1940
of the actinides only U(1789), Th (1829), Ac(1889), Pa (1913) are known

post -1940
The nuclear age ~ uranium and plutonium chemistry

12

1940-1961
Trans-uranium elements synthesized by "bombardment" expts.

Actinides developed as the 5f series equivalent of the

lanthanides (Seaborg's Actinide Concept), & proven not
to be a 4th transition series

post-1955
Lanthanides obtained in increasing amounts ~ increasing technological importance

13

f-orbitals (l=3)
4f Orbitals (General Setting)
fz3 = fz(2z2 - 3x2 - 3y2) [ml = 0]

fxz2 = fx(4z2 - x2 - y2) & fyz2 = fy(4z2 - x2 - y2) [ml = 1]

fxyz & fz(x2-y2) [ml = 2]

fx(x2-3y2) & fy(3x2-y2) [ml = 3]

14

The different f-orbitals are shown here with their representation as general and xyplane projections

15

Why are 4f orbitals filled when they

are?
Thomas-Fermi explanation
The Effective Electron Potential:

Large angular momentum for an f-orbital (l = 3) large centrifugal

potential
tends to keep the electron away from the nucleus Aufbau order

Increased Z increases Coulombic attraction to a larger extent for

smaller n
due to a proportionately greater change in Zeff reasserts Hydrogenic

order
This can be viewed empirically as due to differing penetration effects

Radial Wavefunctions Pn,l2 for 4f, 5d, 6s in Ce

4f orbitals (and the atoms in general) steadily contract across the

lanthanide series
16

Effective electron potential for the excited states of Ba {[Xe] 6s 4f} & La

{[Xe] 6s 5d 4f}
show a `sudden' change in the broadness & depth of the 4f "inner well"

for Ba (Z = 56) 4f is an outer orbital with 4f close to its value

for the H atom
for La (Z = 57) 4f is an inner orbital with 4f ca. 0.7ao
though only for the next atom, Ce (Z = 58) is the 4f
electron of sufficiently high binding energy to appear in
the ground state configuration

17

Which Elements are d-block or f-block?

Most current Periodic tables have:

La as first 5d transition element

Ac as first 6d transition element

Reasons?
possibly erroneous (early) interpretation of atomic spectra misleading
electronic configurations?

Some ground state electronic configurations

Calcium [Ar]4s2 Scandium [Ar]4s23d1
Strontium [Kr]5s2 Yttrium [Kr]5s24d1
Barium [Xe]6s2 Lanthanum [Xe]6s25d1
Ytterbium [Xe]6s24f14 Lutetium [Xe]6s24f145d1
Radium [Rn]7s2 Actinium [Rn]7s26d1
Nobelium [Rn]7s25f14 Lawrencium [Rn]7s25f146d1

In each case: Differentiation by (n-1)d1 ~ as expected for the start of a transition

series

Lutetium and Lawrencium are just as good candidates to be the first

elements of the 3rd and 4th transition series as Lanthanum and Actinium

Some suggestions why Lu might best regarded as the

first 5d transition element.

Periodic Trends in Various Properties

18

 Structures of Metal, Metal Sesquioxide (M2O3) and

Metal Chloride (MCl3)
Similarities for Sc, Y, Lu
Differences from La

Revised Medium-Block Format Periodic

Table
See the article:- W.B. Jensen, The Positions of Lanthanum(Actinium) and
Lutetium(Lawrencium) in the Periodic Table, Journal of Chemical Education, 1982,
59, p. 634-636

19

LANTHANIDES
Abundance & Distribution
Not especially Rare!
except Prometheum (147Pm, t1/2 = 2.6 years) which is produced
artificially
e.g. La, Ce & Nd are more common than Pb
"Rare Earth" label not really justified today

Most-common minerals:
monazite & xenotime (mixed La, Th, Ln phosphates)
widely-distributed, concentrated in sand & river beds
due to relative insolubility

bastnaesite (a La, Ln fluorocarbonate M

III

CO3F)

a vast deposit in Sierra Nevada, USA ~ discovered in

1949 ~ supplies much of world's needs
60-70% of the metal content of these minerals is rare earth oxide

Elemental Proportions of Rare Earth-Content of

Minerals
% of Ln as: Th Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
monazite

ca 6 3 22 45 5 17

4 0.1 2 0.2 1 0.1 0.4 - 0.2 -

xenotime

ca 5 61 0.5 5

0.7 2.2 1.9 0.2 4

basnaesite

0.05 0.1 32 49 4.4 13.5 0.5 0.1 0.3 -

8.6 2

5.4 0.9 6.2 0.4

0.1 -

Abundance of lanthanides in nature

abundance shows even-odd alternation with atomic number

mirrored by several/few alternation of number of stable isotopes with
even/odd Z

21

Due to nuclear shell structure (see : P.A. Cox, The Elements, OUP, 1989, p. 17,
36-44)

Extraction
The extraction of the Lanthanides from minerals is illustrated here by the:-

Alkali Digestion of Monazite/Xenotime

22

Monazite and Xenotime can also be opened-out through an Acid Route

Acid Dissolution of Bastnaesite

The website of Molycorp explains the mining and processing of Bastnaesite at their
Mountain Pass Mine in the Sierra Nevada, USA.

23

Separation
/3 of world production is actually used mixed in the proportions
occuring naturally in the ore

1. Cerium & Europium may be extracted

Chemically:

Oxidize only Ce to M4+ by HClO or KMnO4, then precipitate

as CeO2 or Ce(IO3)4
2+
On action of Zn/Hg only Eu forms a stable M that
doesn't reduce H2O, then isolate by precipitation as EuSO4

2. Separation by Fractionation:
Small Scale methods used originally:
Fractional Crystallization of e.g. Ln(NO3)3.2NH4NO3.4H2O or
Ln(BrO3)3

Fractional Thermal Decomposition of e.g. Ln(NO3)3

Current Small Scale Lab. Separation:
Ion-Exchange Displacement Column

Ln3+(aq) are strongly adsorbed by a cation-exchange

add an eluant

ligand

24

resin

typically chelating ligands

e.g. EDTA
2-hydroxy-EDTA

, or

e.g. HIB{[[alpha]]-hydroxyisobutyric acid}

Ligand binds

most strongly to smallest ion

e.g. the binding constants of the Ln(EDTA) complexes

Elution order is Lu La
The process of separation is indicated graphically

25

greater detail on these columns may be found in:

Greenwood & Earnshaw, p. 1427-1428

Open University S304 Unit 27, p. 20-22

Current Large Scale Industrial Separation:

Solvent Extraction

Ln3+(aq) is extracted in a continuous

counter-current
process into a non-polar organic liquid (e.g. kerosene)

the kerosene contains ca. 10% of

o bis(2-ethylhexyl)phosphinic acid (DEHPA)

or
o

1.
2.
3.

tri-n-butylphosphine oxide (TBPO) (nBu3O)3PO

solubility of Ln3+ in organic solvent increases with its RAM

separation factor for adjacent rare earths = 2.5
automatic multistep, counter-current conditions 99.9% purity Ln

26

The Metals
Production of Elemental Metals
La, Ce, Pr, Nd, Gd:
2MCl3 + 3Ca 2M + 3CaCl2 (T > 1000 C)
Tb, Dy, Ho, Er, Tm, Y:
2MF3 + 3Ca 2M + 3CaF2 (MCl3 is too volatile)
Pm:
PmF3 + 3 Li Pm + 3LiF
Eu, Sm,Yb:
M2O3 + 2La 2M + La2O3 (MCl3 reduced to MCl2 by Ca)
Mischmetall (mixed light Ln) :
electrolysis of fused LnCl3/NaCl with graphite anode &
graphite or steel cathode

Structures of Elemental Metals

Example Structures:View using CrystalMaker

Ce, CCP Structure

27

Gd, HCP Structure

Pr, hc(4H) Structure
Eu, BCC Structure

Properties of the Metals

Silvery white, but tarnish in air

Rather soft (later M are harder)
High mpt & bpt
Very reactive (I1 + I2 + I3) comparatively low
o (reactivity as atomic radius )
+ H2O M2O3 or M(OH)3 & liberates H2 ~ slowly in cold, rapidly
on heating
+ H+ (dilute acid) Ln3+ & liberates H2 ~ rapid at room
temperature
burn easily in air ~ slowly in cold , burn at T > 150 C
o sesquioxides, M2O3
(but Ce CeO2) & (Y is passivated below 1000
C due to its oxide coating)
nitrides, MN
exothermic reaction with H2 MHn (n = 2,3, often results in defect
states)
react readily with C, N2, Si, P, halogens & other non-metals
o

form binaries on heating with most non-metals (e.g. LnN, Ln2S3,

LnB6, LnC2, ...)

Uses of Metals

<1% Mischmetall or Ln silicides improves strength &

workability of low alloy steels for plate and pipes {also used in Mg
alloys}
Mischmetall (50% Ce, 25% La, 25% other light lanthanides) is

pyrophoric ~ alloyed with 30% Fe it is used in lighter flints

28

Chemistry is principally of Ln3+

Why the prevalence of oxidation state III (Ln3+)?
Examine Thermodynamic Parameters:
atmH

I1/2/3/4

hydH(Ln3+)

LH(LnX3)

these values are available in a Table(import DHatm

from larger table for web!)

Ionization
For any given Lanthanide

As successive electrons are removed from neutral Ln the

stabilizing effect on the orbitals is related to their
principal quantum number, 4f > 5d > 6s.
For Ln2+ {except for La & Gd} the configuration is

For Ln3+ the configuration is always [Xe]4f

[Xe]4fn

the 4f binding energy is so great that remaining 4f

electrons are regarded as "core-like" (i.e. incapable of
modification by chemical means) (except Ce)

Note that as a rule of thumb: I4

~ 2 I 3 ~ 4 I2 ~ 8 I1

I4 > (I1 + I2 + I3 )
Therefore in almost all cases Ln3+

best energetics

29

provides the

Observing trends across the Lanthanide Series

The general trend is for increasing ionization energies

with increasing Z (i.e. with increase in Zeff)
Marked Half-Shell Effects - magnitude as n in
In
Also Quarter/Three-Quarter Shell

Effects
(compare with transition metals - these are not seen
clearly with dn configurations)
Explanation?: interelectronic repulsion is related not
just to electron pairing but also to angular

momentum of the electrons

o

e.g. in Pr2+ (4f3) Pr3+ (4f2) ionization removes

repulsion between e- of like rotation, whereas
Pm2+ (4f4) Pm3+ (4f3) removes the stronger
repulsion between e- of unlike rotation ( latter
Ionization Energy is correspondingly lower hence the local minimum in the I3 graph at Pm)

The three-quarter effect is the bigger: interelectronic

repulsion is bigger in smaller Lnn+

30

Atomization
atmH follows the inverse trend to I3 {and therefore
also to (I1 + I2 + I3 ) }
metallic bonding is correlated with ease of
ionization to Ln3+ state
this trend is modified slightly due to the
different structures of the Ln metals

Some Thermodynamic Observations (Ionic Model

style)
The trends in the formation of LnIII
Formation of Compounds {fH(LnX3(s))} or Ln3+(aq)
{E(Ln3+(aq)/Ln(s))}
depend on the balance between:
Energy Supplied to effect Ln(s) Ln(g) Ln3+(g) + 3e-

[atmH + I1

+ I2 + I3]
versus
Energy gained from Ln3+(g) + 3X-(g) LnX3(s) [LH(LnX3(s))] or
Ln3+(g) Ln3+(aq) [hydH(Ln

3+

)]

The energies determining trends in E(Ln3+(aq)/Ln(s)) are graphed below:

31

Production of Ln3+(g) shows

a smooth trend based on size effects (trend based on Zeff)

shell structure effects superimposed with clear maxima at half-shell
(f7) and full-shell (f14)
also smaller quarter and three-quarter shell effects

Hydration Energy of Ln3+ (also Lattice Energies of LnX3(s)) shows

only a smooth ionic-size-based trend (the trend based on Zeff) and

no shell structure effects

Balance of trends in Ionization + Atomization Energies with Hydration

(Lattice) Energy

removes size effects

leaves only the Shell effects - see values of fH(Ln3+(aq))

Overall: The most important energy correlations are

with I3
"exceptions to +3 rule" can also be rationalized
Occurrence of +4 oxidation state
predicted from [atmH

+ I1 + I2 + I3 + I4] which follows trends in I4

32

Ce, Pr Ce4+ [4f0], Pr4+ [4f1] ~ early in series 4f orbitals still

comparatively high in energy

Tb Tb4+ [4f7 valence shell] ~ half shell effect

Occurrence of +2 oxidation state

predicted from [atmH
is reverse of trend in

+ I1 + I2] which follows trends in atmH, which

I3

Eu, Sm, Yb Eu2+ [4f7], Sm2+ [4f6], Yb2+ [4f14]

~ clear influences of electronic shell structure & from atmH

33

General Features of Lanthanide

Chemistry
The general features of lanthanide chemistry are reviewed before they are
examined in more detail

1. similarity in properties, with gradual changes

occurring across the lanthanide series

a size effect from the Lanthanide

Causes:
o

Contraction

Poor screening of nuclear charge by 4f electrons

steady increase in Zeff

Relativistic effects influence the shielding

characteristics of inner electrons

see: K.S. Pitzer, Accounts of Chemical Research, 1974, 12, p.
271-276

2. Primarily the 3+ oxidation state adopted for all

elements

Redox chemistry is commonly encountered only for Eu (3+/2+) and

Ce (4+/3+)

Some solids formulated as LnII compounds actually contain Ln

-

delocalized e

34

3+

&

3. Coordination chemistry is not especially extensive

Chelating ligands are preferred

4. Bonding on coordination is primarily ionic in

character
complexes undergo rapid ligand exchange
Why is the bonding so ionic? 4fn electrons are contracted into
the core and unable to participate in bonding
Other implications from lack of covalent bondforming orbital-availability

no -backbonding occurs

no simple carbonyl species (except in

Ar matrix at 10 K)

cyclopentadienyls are ionic in nature

[c.f. Ln(C5H5)3 vs Fe(C5H5)2]

lanthanide organometallics have

different properties from transition metal
equivalents

5. Ln3+ cations display typical a-class (hard)

properties

preference for O-donor ligands

Qu. Why not N too? Ans. O-donor ligands are more likely to be
charged(importance of ionic bonding to lanthanides!)

6. Binding to water is common

such that H2O is often found included in products isolated from
(aq)

35

7. Coordination numbers are high

>6, typically 8, 9,... (up to 12 found)

8. Coordination polyhedra are often ill-defined

determined by ligand requirements, not by bonding requirements

no confirmed examples of isomerism
Solid state structures of binaries are often rather different from
those of other metals

9. Ligand Field Effects are very small

Pale Colours from weak, narrow forbidden f f optical
transitions
M3+ ions are :

Colourless (La, Ce, Gd, Yb, Lu)

Green (Pr, Tm)
Lilac (Nd, Er)
Yellow Pink (Pm, Ho)
Yellow (Sm, Dy)
Pale Pink (Eu, Tb)

Magnetic properties have spin-orbit coupled

contributions
(spin-orbit coupling >> ligand field splittings)
Ln3+ magnetic moments: 0 B [1S0] to 10.55 B
[5I8]

Magnetic & Optical properties are largely independent of

environment (e.g. similar spectra in gas/solution/solid)
Renewed Technological interest in Lanthanides is mainly in
optical/magnetic materials

36

Solution Chemistry
Solubility

Ln3+ are not especially soluble in water

no simple relationship of solubility to cation radius
o depends on small difference between large solvation and lattice
energies
o depends on entropy effects
oxalates/double sulfates/double nitrates
lighter Ln more soluble
basic nitrates
heavier Ln more soluble
basis of classical separation procedures

Hydrated Lanthanide Ions

Primary hydration numbers in (aq) are 8, 9

from Luminescence & NMR measurements

Primary hydration number with Lanthanide Contraction

Secondary hydration number with Lanthanide Contraction
ry
o increased polarization of 1 hydration sphere by a smaller
cation enhances hydrogen bonding to water in the secondary
hydration sphere
Aqua ions hydrolyze ~ increasingly so from La to Lu as they
become smaller
3+
2+
+
o Ln(H2O)n + H2O Ln(H2O)n-1 + H3O
3+
Salts with common anions frequently contain Ln(H2O)9
with tri-capped trigonal prismatic (ttp)

geometry

Coordination Compounds
37

Strongly complexing, chelating ligands necessary to

yield isolable products from (aq)

Some O-donor chelating ligands that form complexes include:
NO3o
o

binds in its chelate mode

notable for high Coordination Numbers
2! Ce(NO3)5 10-coordinate bicapped dodecahedron
Ce(NO3)63- 12-coordinate icosahedron

Oxalate

Citrate

Tartrate

-diketonates R(CO)(CH-)(CO)R

38

Classic bidentate complexes formed as Ln(L-L)3L' (L' = H2O,

py, etc...) or Ln(L-L)4
o dehydrate Ln(L-L)3(H2O) in vacuo -> Ln(L-L)3 now
coordinatively unsaturated!
o Ln(L-L)3 with bulky R
! thermally stable
! volatile & sublimable
! soluble in non-polar solvents
! Widely used as NMR shift reagents
polar molecules may coordinate {Ln(L-L)3}, their NMR
resonances are perturbed by the paramagnetism of Ln

e.g. Eu(facam)3

"Anti-knock" activity as petroleum

additives

Macrocyclic Ligands
Crown Ethers
o

differing cavity/M sizes allow range of C.N & stoichiometry

e.g. with 18-crown-6

La-Gd

[Ln(18-C-6)(NO3)2]3[Ln(NO3)6]

La-Nd

[Ln(18-C-6)(NO3)3]

12-coordinate

Tb-Lu
[Ln(NO3)3(H2O)3](18-C-6)
coordinated ~ cavity too large
39

10-coordinate

18-C-6 is not

Complexes with
o uncharged monodentate ligands
o ligands with donor atoms other than O

MUST be prepared in the absence of H2O

e.g. Ln(en)43+ (8-coordinate) from polar organic

solvents (e.g. acetone)
(18-crown-6) complexes dissociate instantly in water!

Coordination by halides is weak

but LnX63- (unusually octahedral) are isolable from non-aqueous
solution

Solution Chemistry of Other

Lanthanide Oxidation States
Ln(IV)
Cerium is the only Ln4+ with significant aqueous or coordination
chemistry
E (Ce4+(aq)/Ce3+(aq)) = 1.72 V (others est. 2.9 V)

prepared by the action of a strong oxidizing agent, e.g. S2O82-, on

Ce3+(aq)
widely used as an oxidant itself:- e.g. quantitative analysis / organic
chemistry
E (Ce4+/Ce3+) is markedly dependent on complexation and
hydrolysis
o strong oxidizing agent in perchloric acid solution
o in other acids coordination occurs
e.g. Ce(NO3)62- is generally used for oxidations as its NH4+ salt
o

on pH:
1. hydrolysis to Ce(OH)3+ occurs
2. then polymerization
3. ultimately precipitation of yellow gelatinous CeO2.xH2O

40

4+ charge stabilizes halogeno-complexes e.g. CeF84{aside: CeF62- is 8-coord through fluoride-bridging, but CeCl62- is
octahedral}

Ln(II)
Significant solution chemistry of Ln2+ is essentially confined to Sm
II

Eu , Yb

II

II

Preparation:

electrolytic reduction of Ln3+(aq)

Eu2+ (the most stable LnII) is prepared by reduction of Ln3+(aq) with
Zn/Hg

Properties

Ln2+ Aquo-ion colours

2+
o Sm blood-red
2+
o Eu colourless
2+
o Yb yellow
Ln2+(aq) are readily oxidized by air
2+
o BUT Eu (aq) is easily handled
Sm2+(aq) & Yb2+(aq) reduce water
Eu2+(aq) is relatively stable in the dark
Carbonate and sulfate salts have been isolated
Sm2+ and Yb2+ salts are susceptible to oxidation by their water of
crystallization
Eu & Yb dissolve in l-ammonia to give intense blue, highly
reducing solutions
2+
o contain [Ln(NH3)x] and solvated electrons?
o Solutions decompose on standing, precipitating the amide
Ln(NH2)2
Properties of Ln2+ are closely-related to those of the alkaline earths
In particular Eu2+ is often likened to Ba2+
1. Similar Salt Solubilities (like Ba, sulfates are insoluble,

hydroxides are soluble)

2. Behaviour in l-NH3 is very similar
3. Similar Coordination Chemistry (Not extensive / Hard
ligands)
4. But Very different redox chemistry!
41

Magnetism & Spectra

config. Ground
Ln Ln3+
4f
4f1
4f2
4f3
4f4
4f5
4f6
4f7
4f8
4f9
4f10
4f11
4f12
4f13
4f14

La
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu

No. of

Observed

State unpaired e- Colour

S0
F5/2
3
H4
4
I9/2
5
I4
6
H5/2
7
F0
8
S7/2
7
F6
6
H15/2
5
I8
4
I15/2
3
H6
2
F7/2
1
S0
1

0
1
2
3
4
5
6
7
6
5
4
3
2
1
0

colourless
colourless
green
lilac
pink
yellow
pale pink
colourless
pale pink
yellow
yellow
rose-pink
pale green
colourless
colourless

0
2.54
3.58
3.62
2.68
0.85
0
7.94
9.72
10.65
10.6
9.58
7.56
4.54
0

eff/B
0
2.3 - 2.5
3.4 - 3.6
3.5 - 3.6
1.4 - 1.7
3.3 - 3.5
7.9 - 8.0
9.5 - 9.8
10.4 - 10.6
10.4 - 10.7
9.4 - 9.6
7.1 - 7.6
4.3 - 4.9
0

Magnetic Properties
Paramagnetism
see R.L. Carlin, Magnetochemistry, Springer, N.Y., 1986 Chapter 9 for
a detailed account

Magnetic properties have spin

& orbit contributions

(contrast "spin-only" of transition metals)

Magnetic moments of Ln3+ ions are generally well-described from the

coupling of spin and orbital angular momenta ~ Russell-

Saunders Coupling Scheme

spin orbit coupling constants are typically large (ca. 1000
cm-1)

ligand field effects are very small (ca. 100 cm-1)

42

 only ground J-state is populated

spin-orbit coupling >> ligand field splittings
magnetism is essentially independent of
environment

Magnetic moment of a J-state is expressed by the Land

formula

Sample Land Calculation

e.g

Pr3+ [Xe]4f2

Find Ground State from Hund's Rules

o

Maximum Multiplicity S = 1/2 + 1/2 = 1

2S + 1 =

3
o

Maximum Orbital Angular Momentum L = 3 + 2 = 5

H state
o

Total Angular Momentum J = (L + S), (L + S) - 1, L - S

= 6 , 5, 4
!

Less than half-filled sub-shell Minimum J

=4
{Greater than half-filled sub-shell Maximum J}

43

Experiment?

3.4 - 3.6 B

Ln3+ Magnetic Moments compared with Theory

Experimental _____
Land Formula -Spin-Only Formula - - -

44

Land formula fits well with observed magnetic moments

for all but SmIII and EuIII
Moments of SmIII and EuIII are altered from the Land expression
by temperature-dependent population of low-lying excited Jstate(s)

Uses of Ln3+ Magnetic Moments?

NMR Shift Reagents - paramagnetism of lanthanide ions is utilized to
spread resonances in 1H NMR of organic molecules that coordinate to
lanthanides (see account of Eu(fcam)3)

Ferromagnetism / Anti-Ferromagnetism
/ Ferrimagnetism
see C.N.R. Rao & J. Gopalkrishnan, New Directions in Solid State
Chemistry, CUP, 1986 p. 394-398
West, Solid State Chemistry p. 565-566, 575-578

Lanthanide metals and alloys have interesting ordered magnetism

effects

SmCo5 permanent magnets - FERROMAGNETIC

o
o
o
o
o

light weight
high saturation moments,
high coercivity
high magnetocrystalline anisotropy
Superior performance magnets for magnetic bearings /
couplings / wavetubes & d.c. synchronous motors

45

Garnets
o

Complex oxides A3B2X3O12

A site
B /X sites

distorted cubic environment

octahedral & tetrahedral sites

[unit cell of Garnet contains 128 atoms!]

o

Rare Earth Garnets e.g. Ln3Fe5O12 and Y3Fe5O12

(yttrium iron garnet, YIG)
FERRIMAGNETISM shows an unusual temperaturedependence

as T
o
o

moment to zero at the Condensation

Temperature
above Condensation Temperature moment rises
in the opposite direction to a maximum
moment then to zero at the Curie
Temperature.in the normal manner

46

Reason?

the magnetic moments of the rare earth and

iron ions oppose each other
the rare earth moments dominate at low
temperature
the rare earth moments randomize at a
lower temperature than the iron moments

"Magnetic Bubble" Memories

o
o
o
o

magnetic stripe domains which shrink to smaller cylinders in

an applied field
Called bubbles because they follow the same equations as
soap bubbles
Magnetic Memory since bubble = 1, and lack of bubble = 0
(binary)
'Bubbles' move towards regions of lower field bias and don't
coalesce
! magnetic medium doesn't need to move (unlike disks
or tapes!)
! typically the bubbles are moved along Ni-Fe tracks
Best bubble memory materials are 20 m films of rare-earth
Garnets, Ln3Fe5O12
! Smallest bubble sizes (2-3 m) in
(Sm0.51Lu0.42Y1.21Ca0.86)(Ge0.70Si0.16Fe4.14)O12

47

How a Magnetic Bubble Memory Works

48

Electronic Spectroscopy

Transitions which involve only a redistribution of electrons within the

4f orbitals (f f transitions) are orbitally-forbidden by the Selection
Rules

pale colours of LnIII compounds are usually not very intense

Crystal/Ligand field effects in lanthanide 4f orbitals are virtually

insignificant
4f electrons are well shielded from external charge by
5s2 & 5p6 shells

f f absorption bands are very sharp (useful fingerprinting and

quantitation of LnIII)

[d<->d transitions in transition metal compounds are also

orbitally forbidden, but gain intensity from and are broadened
by the effects of molecular vibrations in distorting the crystal
field]

optical spectra are virtually independent of environment

- similar spectra in gas/solution/solid (sharp lines like
typical gas atom spectra)

Insensitivity of f f transitions of limited use in study of

lanthanide materials

49

CeIII and TbIII have high intensity bands in the UV

due to 4fn
forbidden

4fn-15d1 transitions i.e. f d and therefore not orbitally

why?
n-1 =0 (empty sub-shell) for CeIII = 7 (halffilled sub-shell) for TbIII

Fluorescence / Luminescence
of certain lanthanides e.g. Tb, Ho & Eu [see West, Solid State
Chemistry Chapter 17]

Luminescence:

emission of light by material as a consequence of

its absorbing energy

Photoluminescence:

use of photons for excitation

Photoluminescent materials generally require a host

[H] crystal structure, doped with an activator [A]

{sometimes a second dopant is added to act as a
sensitizer [S]}

Fluorescence:

short time lapse (~ 10-8 s) between excitation

& emission

long decay times luminescence

continues long after excitation source is removed

Phosphorescence:

50

Applications for
Fluorescence/Phosphorescence

e.g. red phosphor in TV tubes from Eu3+ doped into Y2O3

other luminescence colours:3+

o green: Ce in CaS

Eu3+ in SrGa2S4

blue: Eu2+ in (Sr,Mg)2P2O7

mixed red/green/blue effectively white luminescence
o

used in fluorescent lamp coatings to convert blue/UV discharge to

white light

Anti-Stokes Phosphors have the remarkable property of emitting

photons of higher energy than the incident exciting radiation!
e.g. YF3 host doped with Yb3+ as a sensitizer and Er3+ as an
activator can convert incident IR radiation into green luminescence

Luminescence of Eu3+ is used to probe its environment

ligand charges / binding constants / ligand exchange
rates / site symmetry

Ln3+ as a Probe for Ca2+ Sites in Bioinorganic

51

Chemistry
Ln3+ may replace Ca2+ in its binding sites in proteins
Similar ionic radii
Coordination number of Ln3+ (7-9) close to Ca2+

o
o

(6-8)
o

Hard metal ions / Prefer oxygen ligation (Ca2+

bound by O of Glu, Asp, Thr, Ser, H2O...)

o
Ln3+ binds ligands ca. 105x more strongly than

Ca2+

o
o

Ligand exchange rates on Ln3+ are ca. 102x

slower than on Ca2+
When Ln3+ replaces Ca2+ at a catalytic site
reaction rates decrease
(explains mild toxicity of rare earth ions!)

Use of Luminescence Spectra

Eu3+ (green) & Tb3+ (red) luminesce strongly at ca. 296 K
after laser excitation
because excitation may occur strongly to excited ligand
states which are just above the Ln3+ excited states
involved in the luminescence for these ions, which are
therefore easily populated
o

Determine Number of H2O molecules bound to

the active-site metal ion
e.g. for the protein thermolysin

Eu3+ luminescence 1H2O for Ca2+ site 1

52

and 3H2O at sites 3 & 4

The different sites may be replaced

independently with different Ln3+
Energy transfer expts. (e.g. Eu3+Tb3+)

intersite distances
Use of Paramagnetism
o

Ln3+ bound in a metallo- site acts as NMR

shift/relaxation agent
active site protein geometry from 1H
NMR spectra

Use of Electron Density

o

Ln3+ Heavy atom derivatives to assist solving

X-ray diffraction structures

Lasers
One of the most common high power lasers is the Neodymium

YAG laser
o
o
o

Host material is Yttrium Aluminium Garnet (YAG), Y3Al5O12,

doped with Nd3+
Examine the garnet structure (also considered for its magnetic
properties in e.g. YIG)
a '4'-Level Laser System

53

Change of host material makes small differences in

laser radiation frequency
Change of dopant ion makes large changes in laser
radiation frequency

Halides
Halides of the form LnX2, LnX3 & LnX4 {only (Ce,Pr,Tb)F4} exist

LnX4

Only (Ce,
o

Tb, Pr)F4 are known

correlation with I4 of Ln

fluorides only - most oxidizing halogen!

CeF4 is comparatively stable e.g. crystallizes as a monohydrate
from (aq)
TbF4, PrF4 are thermally unstable and oxidize H2O
o i.e. prepare dry!
o

54

MF4 all white solids with the UF4/ZrF4

structure

Dodecahedral coordination of M

LnX3

All LnX3 are known (except Pm {not attempted} & possibly EuI3)
Typically crystalline / high mpt. / deliquescent
Typically obtained as hydrates from (aq)
e.g. La - Nd
7H2O
Nd - Lu

6H2O

On heating, react with water oxyhalides

LnOX + 2HX

LnX3 + H2O

at high temperatures react even with glass

2LnOX + SiX4

2LnX3 + SiO2

Preparation of anhydrous LnX3

LnF3
1. Ln(NO3)3(aq) + 3HF LnF30.5H2O (very insoluble)
2. heat LnF30.5H2O (under an HF atmosphere for heavy Ln)

anhydrous LnF3
LnCl3
3. Ln2O3 / Ln2(CO3)3 + HCl(aq) LnCl36-8H2O (rather soluble)
4. heat LnCl36-8H2O (under HCl atmosphere for heavy Ln)

anhydrous LnCl3
or
Heat at 300C, Ln2O3 + 6NH4Cl 2LnCl3 + 3H2O + 6NH3
55

LnBr3 / LnI3
5. Best by direct

combination (susceptible to hydrolysis to

oxyhalides)
6. purify by sublimation (but avoid contact with hot silica!)

Structures: Ln coordination varies from 9 for light trifluorides to 6

for heavy iodides
e.g.

La - Gd

LnCl3

Tb,
Dy(form I)
Dy-Lu

UCl3
structure
PuBr3
structure
AlCl3
structure

9-coordinate tri-capped trigonal

Ln
prism (ttp)
8-coordinate bi-capped trigonal
Ln
prism (btp)
6-coordinate
octahedron
Ln

Coordination Environments from LnX3 structures

LnX3 structures (and colours)

La

Ce

Pr

Nd

Pm

LaF3 LaF3 LaF3 LaF3

F

Sm

Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

YF3

YF3

YF3

YF3

YF3

YF3

YF3

YF3

YF3

YF3

LaF3?
white white green violet
UCl3

UCl3

white white white white green pink

UCl3 UCl3

UCl3

UCl3

pink white white white

UCl3 PuBr3 AlCl3 AlCl3 AlCl3 AlCl3 AlCl3 AlCl3

UCl3?

Cl
white white green mauve
UCl3

UCl3

yellow yellow white white white yellow violet yellow white white

UCl3 PuBr3 PuBr3 PuBr3 PuBr3 FeCl3 FeCl3 FeCl3 FeCl3 FeCl3 FeCl3 FeCl3 FeCl3

Br
white white green violet
PuBr3 PuBr3
I

yellow grey

white white white yellow violet white white white

PuBr3 PuBr3 FeCl3 FeCl3 FeCl3

PuBr3

white yellow

FeCl3 FeCl3 FeCl3 FeCl3 FeCl3 FeCl3

FeCl3

green

orange

yellow

LnX2
56

green yellow violet yellow white brown

Preparation
Typically from comproportionation:- Ln + 2LnX3 3LnX2
o {(Sm,Eu,Yb)I2 are obtained from thermal decomposition of
LnX3
o (Sm,Yb)I2 from Ln + ICH2CH2I
LnI2 + CH2=CH2 }
LnX2 are easily oxidized
o liberate H2 from H2O {Except for EuX2 }
Occurrence of dihalides
o parallels high values for I3
o depends upon the oxidizing power of the halogen (iodides
most numerous!)
o

Trends in the Stability of MX2

o Consider 3MX2(s)
M(s) + 2MX3(s)
!
!

the reverse of the preparation of MX2

the most likely decomposition route for MX2

mH = 3LH(MX2) - 2LH(MX3) + 2I3 - atmH(M) - (I1 + I2)

!

Irregularities should follow [ 2I3 - - atmH(M) ]

i.e. effectively follow I3 [since variation in atmH follows

closely variation in I3
More? see D.A. Johnson, Some Thermodynamic Aspects of
Inorganic Chemistry, p. 160-162, 165]

57

explains occurrence of MCl2

!
!

La, Ce, Pr MCl2 unknown

(Sm, Eu, Yb)Cl2 are the most stable MCl2
~ may be prepared from LnCl3(s) + 1/2H2 LnCl2(s) +
HCl

!
!
!

Occurrence:
o
o
o

all X
X=Cl,Br,I
X=I only

(Sm,Eu, Yb)
(Nd,Dy,Tm,)
(La,Ce,Pr,Gd)

Structures
o
o
o
o
o

Gd, Tb
low I3 MCl2 unstable to
disproportionation
Nd, Dy, Tm
MCl2 known
Ho, Er
MCl2 unknown

Coordination numbers from 9 to 6 (see: Wells)

Fluorides are Fluorite (CaF2) [C.N. = 8]
Nd,Sm,Eu chlorides are PbCl2type [C.N. = 7 + 2]
Nd,Sm,Eu bromides and iodides are SrBr2 type [mixed C.N.
= 7 & 8]
(Dy,Tm,Yb)I2 have layer structures (CdCl2,CdI2) [C.N. = 6]
polarization effects

Two Classes of Dihalide

1. Most LnX2 are regarded as "salt-like" halides (insulators)
2. (Ce,Pr,Gd)I2 have metallic lustre, high conductivity
o

formulation as Ln3+(I-)2(e-) with the electron in a

delocalized conduction band
! see Cox, Electronic Properties of Solids, {p. 142-145
explanation of metallic LnII compounds}

58

LnII Compounds are finding increasingly more uses

Lower Halides

LnX3/Ln melts yield phases of reduced halide formulae e.g. Ln2X3 &
LnX
"Reduced Halides" contain "condensed metal clusters"
Black & metallic delocalization of electrons through the metalmetal bonded networks

Gd2X3 single chains of edge-sharing metal octahedra with M6X8type environment (i.e. face-capped by X)

59

Lowest Halides are stabilized by H, C or N atoms

encapsulated in Ln6 cluster octahedra
e.g. Gd2Cl2C2

e.g. Gd3Cl3C

Layers of edge-sharing M6C units

Framework of M6C units

60

Hydrides
Preparation: Heat at 300-350C, Ln + H2 LnH2
Properties of LnH2

black, reactive, highly conducting

fluorite structure

61

most thermodynamically stable of all binary metal hydrides

formulated as Ln3+(H )2(e ) with e- delocalized in a metallic
conduction band
further H can often be accommodated in interstitial sites
o

frequently non-stoichiometric
!

e.g. LuHx where x = 1.83-2.23 & 2.78-3.00

high pressure of H2 LnH3

3+
o reduced conductivity: salt-like Ln (H )3

except for Eu and Yb (the most stable LnII)

The Hydrogen Storage Problem

see e.g. C.N.R. Rao & J. Gopalkrishnan, New Directions in Solid State
Chemistry, CUP, 1986 p. 399-405
K. Kosuge, Chemistry of Non-Stoichiometric Compounds, OUP,
1994 p. 219-230

The use of H2 as a fuel is most attractive

Problem: Difficult to store/transport as a liquid

low bpt & low density

H2 forms explosive mixtures with air explosion risk on storage!

Solution: Store hydrogen as a solid compound (hydride) from which

it can be re-extracted

Metals show two common types of hydride-forming behaviour:o Absorb Hydrogen reversibly but in small amounts
e.g. Pd, V, Nb, Ta
o

Absorb large quantities of hydrogen, but, essentially

irreversibly
e.g. rare earths, alkaline earths, Ti, Zr

Intermetallic Alloys between the two classes can be useful for

hydrogen storage

62

e.g. LnNi5 class of alloys

Possible Applications of Rare Earth Intermetallic Hydrides

1. Production of ultrapure hydrogen
2. Isotope Separation of deuterium and hydrogen
3. Source of fuel for motor vehicles
4. Electrodes in Protonic Batteries/Fuel Cells
5. Load Levelling in Power Stations
6. Chemical heat-pump systems
7. Useful hydrogenation agents in organic chemistry
LaNi5

crystallize in the CaCu5 structure

provides 9 interstitial sites for H

63

adsorption-desorption of hydrogen occurs topotactically

o without drastic change in structure
o however, lattice expands by ca. 25%

At a certain pressure, uptake of H2 begins

A large amount of H2 is adsorbed at nearly constant equilibrium
pressure ~ the Plateau Pressure
When the stoichiometry reaches LaNi5H6 further increase in
pressure yields very little extra hydrogen-adsorption {at highest
pressures LaNi5H8.35 is characterized}

Plateau Pressure ca. 2.5 atm at 298 K

o (ideal case ca. 1 atm!)
Desorption is endothermic faster at ca. 140C
Different LnNi5 changes plateau pressures
64

~ log plateau pressure correlates linearly with unit cell volume of the
LnNi5 phase
o

mixtures allow tuning of equilibrium pressure

`designer' compounds

Dependence of Hydrogen Plateau Pressure on

Unit Cell Volume for LaNi5 compounds
{open circles LnCo5, closed circles LnNi5, open triangles LaCo5-xNix}

Hydrides
Binary Oxides

Ln2O3

The most common lanthanide oxide (notable exceptions; CeO2,

Pr6O11, Tb4O7)
Sesquioxides, Ln2O3, adopt three structure types
Strongly Basic
Absorb water / CO2 from air hydroxide / carbonate salts
Pale colours
Properties strongly resemble alkaline earth oxides

A-type
65

light Ln

unusual LnO7 capped-octahedra

B-type

middle Ln
LnO7 units of three types:
o 2 x capped trigonal prisms
o 1 x capped octahedron

B-M2O3 structure is very complex

Densest of M2O3 structure types favoured by increased pressure

66

C-type

heavy Ln
LnO6 units, but not octahedra
(face & body - divacant cubic)

C-type M2O3 is related to Fluorite (MO2) with 1/4 of anions

removed

67

Polymorphism
A (high T)
B (medium T)
C (low T)
See: Wells, Structural Inorganic Chemistry, p. 543-547 for structural details

Ln(OH)3

obtained by action of conc. NaOH on Ln2O3 under hydrothermal

conditions
9-coordinate Ln with tricapped trigonal prismatic (ttp) geometry
basicity increases with Z - correlates with decrease in r(Ln3+)

LnO2

CeO2 (most stable)

Fluorite (CaF2 ) structure
Pr6 O11 , Tb4 O7 (formed at high PO and high temperature)
Range of non-stoichiometric phases between Fluorite LnO2 and Ctype LnO1.5
2

~ intermediate phases were the first known examples of

shear structures
See: Wells, Structural Inorganic Chemistry, p. 226-228 for an
introduction to shear structures

LnO

known for some Ln

Preparation: Comproportionation Ln + Ln2O3 3LnO
NaCl structure
NdO, SmO lustrous golden yellow, conducting formulated as
Ln3+(O2-)(e-)
EuO (dark red), YbO (greyish-white) insulating genuine Ln2+O2-

68

EuO is ferromagnetic and an insulator when pure

[C.N.R. Rao & J. Gopalkrishnan, New Directions in Solid State Chemistry,
2nd ed, CUP, 1996 p. 302-3]

Borides

A variety of binary borides exist

Most important are LnB6

o
o
o

e.g. YB2, YB4, YB6, YB12, YB66

contain B6 octahedral clusters

isomorphous with CaB6
black, metallic conductivity
(c.f. CaB6 white, insulator)

formulated as Ln3+(B62-)(e-)
except EuB6, YbB6 which are Ln2+(B62-)

MT4B4 compounds
o
o
o

M = Sc, Y, Ln, Th, U

T = Ru, Os, Co, Rh, Ir
of current interest for their superconductivity
e.g. CeCo4B4 structure

69

YRh4B4 Tc = 11.3 K
ErRh4B4 Tc = 8.7 K
also ferromagnetic (TCurie = 0.93 K)

Carbides
Class III

Interstitial Carbides
Close-Packed M with C in Octahedral Interstices
e.g. (Tb,Ho,Y)2C

anti-CdCl2 structure

Class II

Occurrence with La - Ho
M3C
C randomly distributed in 1/3 of Octahedral holes in ccp M
M2C3
Pu2C3 structure ~ C2 groups
MC2
CaC2 structure ~ C2 groups
Metallic lustre & conductivity not salt-like
Hydrolysis of (La,Ce)C2 at ambient temperature ethyne, C2H2

Organometallic Chemistry

Organolanthanide chemistry is not as extensive as organotransition

metal chemistry,
Currently receiving a lot of attention, especially inC-H Bond
Activation studies
Primarily ionic in their bonding contracted nature of the 4f valence
orbitals
70

Lanthanides cannot act as -bases Ln-CO compounds are not

stable
Organolanthanides are extremely air & moisture sensitive
~ reflects highly carbanionic character of organic ligand & oxophilicity of
Ln2+/3+

Cyclopentadienides (C5H5- ligand)

Preparation:
Structure:

Also in+2 Oxidation State

Alkyls & Aryls

71

-bonded alkyls & aryls

from metathesis in ether/thf

R = phenyl probably polymeric

R = CH2CMe3 stable as LnR3(thf)2
[LnMe6]3- have been isolated for most Ln

o
o

Mixed Alkyl Cyclopentadienides

C5Me5 (Pentamethyl-cyclopentadienyl) is a common organo-Ln

ligand
o large bulk only 2 C5Me5 may be bound to Ln
o causes major change in structural & chemical properties
o especially novel chemistry in mixed alkyl cyclopentadienides

e.g.

(C5Me5)2LuCH3

catalyzes alkene polymerization (Ziegler-Natta chemistry)

reacts with C-H bonds of extremely low acidity e.g. CH4 !!
Mechanism of Methane Activation?

Cycloctatetraenide M3+(C8H82&endash;)2 Sandwich

Compounds
Preparation:

72

Structure:

pale green crystals

paramagnetic
air & moisture sensitive
planar COT rings
staggered D8d conformation
solvated K+ interacts symmetrically with one COT ring

Arenes
Lanthanide Bis-Arene 'sandwich' compounds

prepared by metal vapour synthesis (MVS) techniques

stable at ambient temperature

Ln0 - such compounds could not be expected for LnIII with contracted
4f orbitals

For more on Lanthanide Organometallics see: R.D. Khn et al, in Encyclopedia of

Inorganic Chemistry, ed. R.B. King pp. 3618-3666

Comparisons and Contrasts

Yttrium - Why consider it with the Lanthanides?
73

Occurs with lanthanides in rare earth minerals, e.g. monazite

Y occurs effectively exclusively in +3 oxidation state
combines with non-metals YHal3 Y2O3 , Y3+(H-)2(e-),
YH3, etc...

Y3+ has same radius as Ho3+ and is difficult to separate from it

Forms complexes of high coordination number with chelating Odonors, e.g. Y(acac)3(H2O)
Typical organometallics include: Y(C5H5)3 (polymeric in the solid
state)
dimeric Y(C5H5)2Cl, monomeric form is a thf adduct

Scandium too?
6 Reasons why Scandium could be considered with the Lanthanides

1. Sc occurs effectively exclusively in +3 oxidation state

combines with non-metals ScHal3 Sc2O3, etc...
but coordination octahedral (small
size)

2. Sc forms reduced halides e.g. Sc7Cl12 which is Sc3+(Sc6Cl12)3- with Sc6

clusters (but c.f. Nb)

3. Scandium Hydride ScH2 is highly conducting Sc3+(H-)2(e-)

4. Forms complexes of high coordination number with chelating Odonors
e.g. Na+[Sc(CF3COCHCOCF3)4-] with C.N. = 8

but forms octahedral complexes

with monodentate ligands e.g. merScCl3(thf)3

5. Nitrate & Sulphate are obtained as hydrated salts Sc(NO3)34H2O &

Sc2(SO4)35H2O

6. Typical organometallics include: Sc(C5H5)3 (polymeric in the solid state)

74

dimeric Sc(C5H5)2Cl, monomeric form is a thf

adduct

6 Reasons why Scandium could be considered as main group IIIA

1. Sc3+ (r = 74 pm) is appreciably smaller than any of the rare earths

behaviour intermediate between the Lanthanides &
Aluminium

2. Sc2O3 is more like Al2O3 than Ln2O3: amphoteric Sc(OH)63- in excess

OH-

3. ScF3 disssolves in excess F- ScF63- (N.B. scarcity of halogeno complexes

for Lanthanides)

4. Anhydrous ScCl3 is easily obtained by P2O5-dehydration of hydrated

halide
but unlike AlCl3, ScCl3 is not a Friedel-Crafts
catalyst

Scandium may with similarly few exceptions be viewed as a 1st Row

Transition Metal

Six-coordinate complexes are typical

Aqua-ion is Sc(H2O)63+ and is susceptible to hydrolysis O-Hbridged dimers...

Some CONTRASTS between Lanthanides & PreTransition & Transition Metals

Pre-Transition
Metals
Essentially
Monovalent

Lanthanides

Transition Metals

Essentially
Monovalent (+3)

Show Variable Valence

- show Group (n+)

+2/+4 for certain

75

(extensive redox chemistry)

oxidation state

configurations

control by environment ~ ligands,

pH etc

Lanthanide
Contraction of Ln3+

Size changes of Mn+ less

marked

Similar Properties

Substantial Gradation in
Properties

Periodic trends
- dominated by
(effective nuclear)
charge
at noble gas config.
(i.e. on group valence)

Similar Properties
for a given group
(differentiated by size)

(differentiated by size)

No Ligand Field
Effects
Always 'hard' (O,
Hal, N donors)

common
diverse mineralogy
mineralogy
Substantial Ligand Field
Insignificant
Ligand Field Effects
Effects
Always 'hard' (O,
Later (increasingly from
Hal, N donors) Fe&endash;Cu)/heavier metals

(preferably negatively
charged)

(preferably negatively
charged)

may show a 'soft' side

'Ionic' 'Covalent'
Organometallics

'Ionic'
Organometallics

'Covalent' Organometallics

No -Ligand Effects

Paucity of -Ligand
Effects

widespread on earth

Poor Coordination High Coordination

Properties
Numbers

-Acceptor Ligands
Extensive Chemistry
Extensive Coordination
C.N. = 6 is typical maximum

(C.N. determined by
size)

(C.N. determined by
size)

Flexibility in
Geometry
No Magnetism from
the metal ions

Flexibility in
Geometry
Free Ion-like
Magnetism

- noble gas
configurations of ions

ground state
magnetism

excited J-states populated

'Ionic' compound
formulations

Weak, Narrow
Optical Spectra

Stronger, Broader Optical

Spectra

76

(but many exceptions)

Fixed (by Ligand Field effects)

Geometries
Orbital Magnetism
'Quenched' by Ligand Fields

 large HOMOLUMO gaps

forbidden,
unfacilitated
transitions

UV CT spectra

77

forbidden transitions vibronicallyassisted

ACTINIDES
Periodicity
Actinides is taken here to mean the 15 Elements from Actinium (Ac)
to Lawrencium (Lr)

q.v. argument as to whether Ac or Lr is the first 4th Transition Series element

Electronic subshells are filled in a manner analagous to the lanthanide

series

Ac

Th

Pa

Np

Pu

Am

Cm

Bk

Cf

Es

Fm

Md

No

Lr

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

6d7s 6d27s 5f26d7s 5f36d7s 5f46d7s 5f67s 5f77s 5f76d7s 5f97s 5f107s 5f117s 12 2 (5f137s2 (5f147s2 (5f146d7s2
5f 7s
M(g) 2
2
2
2
2
2
2
2
2
2
)
)
)
2
M+(g) 7s2

6d7s2 5f27s2

5f37s2

5f57s?

5f67s 5f77s 5f77s2

5f97s 5f107s 5f117s

(5f127s
(5f137s) (5f147s) (5f147s2)
)

M2+(g
7s
)

5f6d 5f26d

5f36d?

5f5?

5f6

5f7

5f8

5f9

5f10

5f11

(5f12)

(5f13)

(5f14)

(5f147s)

M3+(g
)

5f

5f2

5f3

5f4

5f5

5f6

5f7

5f8

5f9

5f10

(5f11)

(5f12)

(5f13)

(5f14)

5f

5f2

5f3

5f4

5f5

5f6

5f7

5f8

(5f9)

(5f10)

(5f11)

(5f12)

(5f13)

M4+(g
)

i.e. the Actinides are the second row of the f-block (5f series)
The Actinide Concept of Seaborg - proposed only in 1944
o

prior to the synthesis of trans-uranium elements only the

chemistries of Th and U were much studied ~ leading to
assignment as a 4th transition series elements

Naturally Occurring Actinides

Only Actinium, Thorium, Protactinium & Uranium occur

naturally (i.e. Z 92)
o Actinium & Protactinium occur only in trace amounts

79

Neptunium & Plutonium occur in uranium minerals in

minute amounts
~ not appreciated until after they had been synthesised that the
synthesis route might occur naturally!

All isotopes of all the actinides are radioactive

Most of the longer-lived isotopes decay by -emission
Half-lives Only quantities of 232Th, 235U, 238U {and possibly 244Pu}
could have survived since the formation of the solar system
Both Thorium and Uranium are far from rare
Thorium
o
o
o
o
o

Widely dispersed, accounts for >3 ppm of the earth's crust

Natural Thorium is essentially 100% 232Th
Occurs in monazite [with the rare earths] and in uranothorite
[a mixed Th,U silicate]
Obtained as ThO2, thoria, from mineral extraction process
Used as 99% ThO2 / 1% CeO2 in thoria gas mantles

Uranium
Widely distributed - found scattered in the faults of old
igneous rocks
238
o Natural Uranium is 99.27%
U & 0.72% 235U
o Obtained usually as UO2
o Used for nuclear fuel, and on a smaller scale for colouring
glass/ceramics
Basic Features of Nuclear Structure & Chemistry and
Radiochemistry
o

excellent, straightforward introduction: Sharpe, Inorganic Chemistry,

Chapter 1
o aspects of nuclear structure and stability: P.A. Cox, The Elements,
OUP, 1989, Chapter 2
o

3 Decay series explain features of the occurrence, distribution &

discovery of actinide elements

Uranium Decay Series (from 238U)

Actinium Decay Series (from 235U)

80

Thorium Decay Series (from 232Th)

All Radon isotopes are short half-life -emitters (but

give rise to short-lived -emitters)
Radon gas is derived from Thorium content in
Granite minerals hazard in igneous areas

Actinium and Protactinium occur in uranium ores in

trace amounts, because of their participation in
Actinium Decay series (from 235U)
In fact Protactinium was originally found by
Fajans & Ghring (1913) as Brevium, 234Pa (T1/2
= 6.8 h), in the uranium (238U) decay series
before Hahn & Meitner and Soddy & Cranston
(1916) discovered the much longer-lived 231Pa
(T1/2 = 33,000 y) in the actinium (235U) decay
series. Named Protactinium because it is the
parent of actinium in the decay series from 235U

Synthesis of Trans-Uranium Elements

1932 Chadwick discovers the neutron
1930s Fermi realises that neutron capture by heavy elements is often

followed by -emission (& -ray production) leading to (Z+1) element.

However neutron-bombardment of 238U yields mainly fission

products

1940 McMillan & Abelson identify tiny amounts of a short-lived isotope

of element 93

81

1940-60 The Golden Age of Element Synthesis through various

"bombardment" techniques

Principal investigators: G.T. Seaborg & A. Ghiorso

Bombardment particles include:Neutrons,

, Deuterons,

,-particles,

Carbon nuclei,

Production of elements beyond Pu requires successive neutron

capture
e.g.

reasonable yields need high neutron fluxes

where are the highest neutron fluxes? - in a
thermonuclear explosion!
hence the discovery of Es & Fm from
debris of such an explosion

Heaviest elements are (more conveniently!) made by heavy ion

bombardment
e.g.

Problems with heavy ion bombardments include:o

Principal Difficulties associated with Heavy Element Isolation &

Characterization
1. Powerful accelerators needed for appropriate velocities (inertia
mass)
2. Products are produced only an atom at a time!
3. Individual elements are not produced cleanly in isolation
separation from other actinides & from lanthanide
fission products
82

4. Radioactivity
remote-handling often necessary (Actinides are also
highly toxic)
damage to solutions
e.g. generation of radicals, H, OH in H2O

leads to reduction of higher Actinide

oxidation states

heating problems (e.g. 242Cm gives out 122 Wg-1)

problems with crystallography
o
o

fogging of X-ray film

creates defects in crystals

5. Instability of most nuclides ~ e.g. No (T1/2 = 1 hr) & Lw (T1/2 = 3

min)
Heavier elements ( Bk) are produced only in the
minutest amounts
o

e.g. typical yields of 258Md (T1/2 = 3 m) are 1 to 3

atoms per expt.!

only a few atoms of No and Lr have ever been
isolated

Timespan available for experiments can be very

limited
6. Difficulty in identification of a few atoms
o

Separation by ion-exchange techniques (c.f. lanthanides)

even after purification cumulative daughter
product contamination may be a problem

Using nuclear decay statistics to detect and count the atoms

prediction of behaviour from utilization of
decay systematics

Chemical Tracer methods

83

 need for accurate prediction of properties

o

Pure chemical properties (where accessible) performed on oxide

samples confined in quartz capillaries attached to high-vacuum
systems

computer-controlled apparatus for

study of transuranic chemistry

For a fascinating account of heavy actinides, including personal

recollections of the experiments
see: G.T. Seaborg & W.D. Loveland, The Elements beyond Uranium,
Wiley, N.Y., 1990

Are there any uses for trans-Uranium

elements?
Principal Actinide Isotopes Available in Macroscopic
Quantities
Isotope
232

Th

231

Pa

HalfLife
1.39 x
1010 y
3.28 x
105 y

Source

Quantities

Natural (100% abundance)

k. tonnes

Natural (0.34 ppm in uranium ores)

grams

84

7.13 x
Natural (0.7204% abundance)
105 y
4.5 x
Natural (99.2739% abundance)
109 y
2.2 x
106 y
86.4 y
24,360
y

235

238

237

Np

238

Pu

239

Pu

241

Am

433 y

kg

243

Am

7650 y

kg

243

Cm

18.12 y

kg

249

Bk

252

Cf

325
days
2.57 y

k. tonnes
k. tonnes
multi kg
kg
k. tonnes

mg
mg

Other long-lived isotopes are known, but generally only

obtained in traces

Plutonium:
239

Pu

produced from 238U by neutron capture in all nuclear reactors

acts as nuclear fuel in fast-breeder reactors
processed for nuclear weapon applications

238

Pu

produced by
used as a compact energy source due to the heat from -decay
N.B. -emission is harmless, unless the emitter is ingested

deep-sea diving suits are heated by ca. 750g of 238Pu

combined with PbTe thermoelectric totally reliable
electricity

85

used in Apollo space missions / Human

heart pacemakers

Americium:
241

Am is used as the -emission source in smoke alarms

Actinide Metals
Preparation
General method for all Actinides:
Reduction of AnF3 or AnF4 with vapours of Li,
Mg, Ca or Ba at 1100 - 1400C

Highly Electropositive
Typically react with:

air tarnishing
boiling water or dilute acid releasing Hydrogen
most non-metals in direct combination

Structures
Very dense metals (e.g. U 19 gcm-3) with distinctive
structures
e.g. Plutonium has at least 6 allotropes and forms
numerous alloys
Plutonium

bc
Symmetry monoclinic monoclinic orthorhombic fcc
tetragonal
315- 457Stability < 122C 122-207C 207-315C
457C 479C

/ gcm-3

16.51

19.86

17.70

17.14

86

15.92 16.00

bcc
479640C

General Observations (comparisons with

Lanthanides)

Electronic Configurations of Actinides are not always easy to

confirm
o atomic spectra of heavy elements are very difficult to interpret
in terms of configuration
Competition between 5fn7s2 and 5fn-16d7s2 configurations is of
interest
o for early actinides promotion 5f 6d occurs to provide more
bonding electrons
much easier than corresponding 4f 5d promotion in
lanthanides

second half of actinide series resemble lanthanides more

closely
5f orbitals have greater extension wrt 7s and 7p than do 4f relative to
o

6s and 6p orbitals

e.g. ESR evidence for covalent bonding contribution in UF3, but not
in NdF3

5f / 6d / 7s / 7p orbitals are of comparable energies over a range of

atomic numbers
o especially U - Am

tendency towards variable valency

greater tendency towards (covalent) complex formation

than for lanthanides, including complexation with -bonding

ligands

electronic structure of an element in a given oxidation

state may vary between compounds and in solution

often impossible to say which orbitals are being utilized

in bonding

Ionic Radii of ions show a clear "Actinide Contraction"

o Actinide 3+ or 4+ ions with similar radii to their Lanthanide
counterparts show similarities in properties that depend upon
ionic radius
87

Electronic Spectra
o narrow bands (compared to transition metal spectra)
o relatively uninfluenced by ligand field effects
o intensities are ca. 10x those of lanthanide bands
o complex to interpret

Optical Absorption Spectrum of U4+(aq)

Magnetic Properties
o hard to interpret
o spin-orbit coupling is large
& Russell-Saunders (L.S) Coupling scheme
doesn't work
o

ligand field effects are expected where 5f orbitals are

involved in bonding

88

Survey of Actinide Oxidation States

The known oxidation states of the actinides are indicated and surveyed:
[importance:

>

>

7
6
5
4
3
2
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

+2

Unusual oxidation state

Common only for the heaviest elements
No2+ & Md2+ are more stable than Eu2+
Actinide An2+ ions have similar properties to Lanthanide Ln2+ and to
Ba2+ ions
rationalization of stabilities: Open University Course Book p. 54-56

+3

The most common oxidation state

The most stable oxidation state for all trans-Americium elements
(except No?)
Of marginal stability for early actinides Th, Pa, U (But: Group
oxidation state for Ac)
General properties resemble Ln3+ and are size-dependent
o stability constants of complex formation are similar for same
size An3+ & Ln3+
o isomorphism is common
3+
3+
o later An & Ln must be separated by ion-exchange/solvent
extraction
Binary Halides, MX3 easily prepared, & easily hydrolysed to MOX
Binary Oxides, M2O3 known for Ac, Th and trans-Am elements

+4
89

Principal oxidation state for Th

Th4+ chemistry shows resemblance to Zr4+ / Hf4+ - is it a
transition metal?

Very important, stable state for Pa, U, Pu

Am, Cm, Bk & Cf are increasingly easily reduced - only stable in
certain complexes
e.g. Bk4+ is more oxidizing than Ce4+

MO2 known from Th to Cf (fluorite structure)

MF4 are isostructural with lanthanide tetrafluorides
MCl4 only known for Th, Pa, U & Np
Hydrolysis / Complexation / Disproportionation are all important in
(aq)

+5

Principal state for Pa

Pa5+ chemistry resembles that of Nb5+ / Ta5+ - is it a
transition metal?

For U, Np, Pu and Am the AnO2+ ion is known (i.e. quite unlike
Nb/Ta)
Comparatively few other AnV species are known
e.g. fluorides, PaF5, NbF5, UF5; fluoro-anions, AnF6-,

AnF72-, AnF83-

e.g. oxochlorides, PaOCl3, UOCl3; uranates, NaUO3

+6

AnO22+ ions are important for U, Np, Pu, Am

UO22+ is the most stable

Few other compounds e.g. AnF6 (An = U, Np, Pu), UCl6, UOF4 etc...,
U(OR)6

+7
90

Only the marginally stable oxo-anions of Np and Pu, e.g. AnO53-

Actinide Aqueous Chemistry

Frost Diagrams for Actinides

Latimer & Frost Diagrams for elements in acid & alkaline (aq) indicate
91

actinides are quite electropositive

Pa - Pu show significant redox chemistry
e.g. all 4 oxidation states of Pu can co-exist in

appropriate conditions in (aq)

stability of high oxidation states peaks at U (Np)

An3+ is the maximum oxidation state for (Cf)Es - Lr
No2+(aq) is especially stable ~ most stable state for No in (aq)
redox potentials show strong dependence on pH (data for Ac - Cm)
o high oxidation states are more stable in basic conditions
o even at low pH hydrolysis occurs formation of polymeric
ions
when hydrolysis leads to precipitation
measurement of potentials is difficult!
e.g. Pa5+ hydrolyses easily; potentials that

indicate it to be the most stable oxidation state

are recorded in presence of F- or C2O42o

tendency to disproportionation is particularly dependent on pH

e.g. at high pH 3Pu4+ + 2H2O

4H+

PuO22+ + 2Pu3+ +

early actinides have a tendency to form complexes

o ~ complex formation influences reduction potentials
e.g. Am4+(aq) only exists when complexed by
fluoride (15 M NH4F(aq))

radiation-induced solvent decomposition produces H and OH

radicals
which lead to reduction of higher oxidation states e.g.
PuV/VI, AmIV/VI

Stability of Actinide ions in aqueous solution:

Ion
Md2+
No2+

Colour

Stability
easy to oxidize, but
stable to water
stable

92

Preparation
Zn or Cr2+ on
Md3+
normal oxdn state
in acid

Ac3+
3+

Np3+
Pu3+

colourless stable
claret
bluepurple
blueviolet

Am3+

pink

Cm3+

pale
yellow

Bk3+

green

Cf3+

green

evolves H2 on
standing; easily
oxidized by air
stable to water; easily
oxidized by air
stable to water & air;
readily oxidized
stable; difficult to
oxidize
stable; chemical
oxidation not possible
stable; can be oxidized
to Bk4+
stable

Es3+

stable

Fm3+

stable

Md3+

stable, but easily

reduced to Md2+

No3+

easily reduced to No2+

Lr3+

stable

Th4+

colourless stable

Pa4+

colourless

U4+

green

Np4+

yellowgreen

stable to water; easily

oxidized
stable to water; easily
oxidized by air to
UO22+
stable to water; slowly
oxidized by air to
NpO2+

93

normal oxdn state

in acid
Na or Zn/Hg on
UO22+
Zn/Hg or H2(Pt)
reduction
SO2 or NH2OH
reduction
I&endash;, SO2 , etc...
on higher states
normal oxdn state
in acid
normal oxdn state
in acid
normal oxdn state
in acid
normal oxdn state
in acid
normal oxdn state
in acid
normal oxdn state
in acid
CeIV or BrO3&endash;
on No2+
normal oxdn state
in acid
normal oxdn state
in acid
Zn/Hg on PaV(aq)
Zn/Hg on UO22+
SO2 on NpO2+ in
H2SO4

4+

Pu

Am4+

Cm4+
Bk4+

Pa5+

stable in 6M acid,
tan-brown disproportionates at
higher pH
only stable as fluoride
pink?
complex; easily
reduced
only as fluoride
pale
complex; stable only 1
yellow
hr at 25C
marginally stable;
yellow
easily reduced
colourless

UO2+

stable; readily
hydrolyzed
unstable to
disproportionation
(least at pH 2-4)
stable;
disproportionates at
high acidity
tends to
disproportionate (least
at low pH)
disproportionates in
acid; reduced by its decay

NpO2+

green

PuO2+

pinkpurple

AmO2+

yellow

UO22+

yellow

stable; difficult to
reduce

NpO22+

pink-red

stable; easy to reduce

PuO22+

orangepink

AmO22+

rumbrown

NpO53-

deep

SO2 or NO2&endash;
on PuO22+
Am(OH)4 in 15 M
NH4F
CmF4 in 15 M
CsF

normal oxdn state

in acid
a transient species

hot HNO3 on Np4+

NH2OH on PuO22+
ClO&endash; or cold
S2O82-on Am3+
oxidation by air in
HNO3
oxidation by CeIV,
MnO4&endash;,
BrO3&endash; , etc.

stable; easy to reduce;

reduced by its decay
easy to reduce; rapidly
reduced by its decay

oxidation by CeIV,
MnO4&endash;,
BrO3&endash; , etc.

only in alkaline

O3 or S2O82- on

94

oxidation by CeIV,
MnO4&endash;,
BrO3&endash; , etc.

green
deep
green

PuO53-

solution
only in alkaline
solution; oxidizes
water

NpO22+ + alkali
O3 or S2O82- on
PuO22+ + alkali

Colour omission concentrated enough solution to tell colour has not

been obtained

Actinide Stereochemistries

Actinide Stereochemistries show similarities with the Lanthanides

o High coordination numbers
e.g. [Th(NO3)6]2- has distorted icosahedral (C.N. = 12)

geometry
e.g. C.N. = 8, 9 are very common UF82-, Th(S2CNEt2)4,

Th(trop)4(H2O)
o

Distortions from idealised stereochemistries

e.g. PuF62- is not octahedral

but widest range of stereochemistries is for An(IV) rather than

An(III)
{possibly because chemistry of early actinides has received
most attention!}

Complexes
o a wide range of complexes with monodentate and chelating
ligands
2+
+
5+
4+
3+
o complexing ability:- [M ] > M > MO2 > M > MO2
uni-negative: F- > NO3> Cl- > ClO4bi-negative: CO32- >
C2O42- > SO42o

geometry may be strongly influenced by covalent bonding

effects
95

e.g. MO22+ unit is always linear UO2(2-NO3)2(H2O)2 is

hexagonal bipyramidal

Compounds Actinide Hydrides, Halides, Oxides, Oxyhalides,...

o for a given oxidation state show similarly diverse C.N. to
Lanthanides
o different accessible oxidation states even greater diversity of
structure
Wide variety of oxidation states of ligands & number of oxidation
states
Extraordinary range of stereochemistry in actinide complexes
and compounds

Stereochemistry of Actinides in Well-Defined Complexes and

Crystalline Solids
C.N. Geometry
distorted
4

O.N. e.g.
+4
U(NPh2)4

distorted tbp

+4

U2(NEt2)8

octahedral

+3
+4

An(H2O)63+, An(acac)3
UCl62-

+5

UF6&endash, -UF5
AnF6
Li5[AnO6] (An = Np, Pu)
Li4UO5 , UO3

distorted octahedral

+6
+7
+6

+5/+6 U5O8
+6
UO2(S2CNEt2)2(ONMe3)
8

cubic
square antiprismatic
dodecahedral
bicapped trigonal prismatic

+4
+5
+4

(Et4N)4[U(NCS)8], ThO2, UO2

AnF83ThI4, U(acac)4, Cs4[U(NCS)8],

+5

-UF5
Th(ox)44-, Th(S2CNEt2)4
PuBr3

+4
+3

96

hexagonal bipyramidal

+6

+6

UO2(2-NO3)2(H2O)2
UF82-

tricapped trigonal prismatic

capped square antiprismatic

+3
+4

UCl3
Th(trop)4(H2O)

10

bicapped square antiprismatic

+4

KTh(ox)4.4H2O

11? fully capped trigonal prismatic? +3

12

UF3

irregular icosahedral

+4

Th(NO3)62-

distorted cuboctahedral

+4

An(3-BH4)4, (Np, Pu)

+4

An(3-BH4)4, (Th, Pa, U)

14? complex

97

Uranium Chemistry
Halides

Fluorides
UF6

The most important fluoride

preparation:
UO2 + 4HF UF4 + 2H2O
3UF4 + 2ClF3 (from Cl2 + 3F2 2ClF3) 3UF6 + Cl2

properties:
o mpt. 64C, vapour pressure = 115 mmHg at 25C
o made on a large scale to separate uranium isotopes
235
! gas diffusion or centrifugation separates
UF6 from
238
UF6
235
! uranium richer in
U is termed enriched, richer in 238U
depleted
! U.K. capacity (BNFL) = 6 kilotonne per year
98

powerful fluorinating agent, e.g. + CS2 SF4

Other Fluorides

UF6 + Me3SiCl Me3SiF + 1/2Cl2 + UF5 (melts to an electricallyconducting liquid)

UF6 + 2Me3SiCl 2Me3SiF + Cl2 + UF4 500-600C UO2 +
CFCl2CFCl2
Mixed-Valence fluorides such as U2F9 also form
Reduction of UF4 with 1/2H2 yields UF3
o LaF3 structure
o like LnF3 is insoluble in water

Chlorides
UCl4

is the usual starting material for the synthesis of other UIV

compounds
preparation: liquid-phase chlorination of UO3 by refluxing
hexachloropropene
properties:
o soluble in polar organic solvents & in water
o forms various adducts (2 - 7 molecules) with O and N donors
e.g. UCl4(CH3CN)4 ~ an ideal dodecahedron
but UCl4(DMSO)3 is actually [UCl2(DMSO)6]2+UCl62-

UCl3

Usually encountered as UCl3(thf)x (a rather intractable material)

Unsolvated binary gives its name to the UCl3 structure!
Actinide trihalides form a group with strong similarities (excepting
redox behaviour) to the lanthanides

UCl6

From chlorination of U3O8 + C

Highly oxidizing
Moisture-sensitive : UCl6 + 2H2O UO2Cl2 (Uranyl Chloride) +
4HCl
In CH2Cl2 solution UCl6 decomposes to U2Cl10 (Mo2Cl10 structure)

99

Halogeno Complexes

All Halides can form halogeno complexes, but F- and Cl- are bestknown
Preparation: from UXx + NaX in melts or solvents (e.g. SOCl2), but
in water only for some fluorides
Occurrence:
III
22III
o U : UCl5 , U2Cl7 and UCl4 (a useful U reagent)
o

UIV: UF73- and UF84- are common, UF62- and UCl62- are also
known
also pseudohalide complexes, e.g. [U(NCS)8]4-

UV: UV is usually unstable in (aq),

but UF5 in 48% HF M+UF6- (M+ = Rb+, Cs+,
H3O+) salts
also UCl6- and UCl63-

UVI: UF7- and UF82- are known, the latter is more thermallystable

Hydrides
Principal Uranium Hydride is UH3
~ important as a source material for UIII and UIV chemistry

100

Oxides

Many binary phases UOx have been reported

o many are not genuine phases
o genuine phases show range of O-content
The most important genuine phases are UO2, U4O9,

U3O8, UO3

UO2 & U4O9 (UO2.25)

UO2 (black-brown) has the Fluorite structure

stoichiometric material is best obtained from:-

Interstitial Oxide Ions may be incorporated into the structure

UO2+x
e.g. Octahedral hole at (1/2,1/2,1/2) is an obvious interstitial location
but Neutron Diffraction studies indicate:
1. oxide vacancies in the normal fluorite lattice
101

2. two types of interstitial sites, O' and O''

displaced from the nominal (1/2,1/2,1/2) position

3. 2O', 2O'' and 2 vacancies cluster together to form
a defect 2 : 2 : 2 Willis Cluster

At UO2.25 (U4O9) (black) the interstitials are ordered forming a

distinct phase in the phase diagram

U3O8 (UO2.67) & UO3

U3O8 (dark green)

conveniently made by heating uranyl nitrate or ethanoate in air

> 650C Higher uranium oxides decompose to U3O8

> 800C U3O8 loses oxygen

102

Structure:
5.33
o Mixed oxide - average oxidation state U
o Evidence suggests Class II/III mixed valence
0.67
o i.e. each Uranium has a time-averaged configuration [Rn]5f
o An orthorhombic, pillared-layer structure
o All U atoms have essentially identical environments
o Contains pentagonal bipyramidal UO7 units

UO3 (orange yellow)

produced by a variety of methods:-

Structure:
o > 6 modifications have been characterised
o Most contain O=U=O 'uranyl' groups linked by 4x
equatorial bridging O
distorted octahedral

environments

Uranates
Fusion of uranium oxides with alkali or alkaline earth carbonates
orange/yellow/brown mixed-oxides, Uranates

103

Aqueous Chemistry

Complex aqueous chemistry due to:o extensive possibilities for complexation

o hydrolytic reactions, often leading to polymeric ion species
Reduction Potentials appropriate for 1M HClO4 indicate:

U3+

powerful reducing agent, reduces H2O to H2 (solutions in 1M HCl

stable for days)
obtained by reduction of UO22+ electrolytically or with Zn/Hg
UF3H2O & U2(SO4)35H2O can be obtained from appropriate
solutions

U4+

only slightly hydrolysed in 1M acid solution U4+ + H2O

H+

U(OH)3+ +

but, it can give rise to polymeric species in less acid

solutions

regarded as a 'stable' oxidation state of uranium in (aq)

UO2+

extremely unstable to disproportionation

evidence for its existence in (aq) from stopped-flow techniques
more stable in DMSO (half-life ~ 30 mins)

104

UO22+

the Uranyl ion

very stable
forms many complexes
a dominant feature of uranium chemistry
reduced to U4+ by e.g. Zinc, Cr2+
2+
18
18
o re-oxidation by H2 O2 U O2
2+
18
18 16
o re-oxidation by O2 U( O O)
linear, symmetrical (O=U=O)2+ structure
Why is UO22+ trans linear, whereas WO22+ is cis, bent?
o
o
o

WO22+ (6d0)is cis, bent because it allows -donation from the

2 O to 2 independent d-orbitals, with a single d-orbital shared
ThO2 (6d05f0) is bent (122deg.) for similar reasons i.e. no forbital participation
UO22+ (6d05f0) is trans, linear because of the participation of
its 5f orbitals
U(5f) are of considerably lower energy than Th(5f) - see section 1

Details of the MO diagram for AnO22+ are controversial,

but f-orbitals have ungerade symmetry, d-orbitals are
gerade
no d-f mixing in centrosymmetric
AnO22+ unit

UO22+ readily adds 4-6 donors in its equatorial plane distinctive

complexes
e.g. cyclic hexadentates strong complexes
e.g. Uranyl nitrate hydrates all contain the

UO2(NO3)2(H2O)2 unit

105

extraction of uranyl nitrate from aqueous nitric

acid into non-polar solvents is a classic
separation method

UO22+ salts show characteristic (yellow) fluorescence

Nuclear Reactors, Atomic Energy &

Uranium Chemistry
Principles of Nuclear Reactors

Nuclear fission = large nucleus splitting into 2 highly energetic

smaller nuclei + neutrons

Sufficient neutrons of suitable energy can induce fission of further
nuclei Chain reaction
to sustain chain reaction a critical mass of uranium
must be achieved (prevents neutron loss)

Kinetic energy of main fragments is converted to heat (106x energy

of same mass of coal)
Only naturally-occurring fissile nucleus is 235U (0.72 % natural
abundance)

' Fast' neutrons produced by fission are not very effective in

producing further fission
either
or

increase proportion of 235U in fuel

slow down (moderate) the fast neutrons

106

~ necessary
anyway to
balance the chain
reaction & prevent
explosion

First self-sustaining nuclear 'reactor' built in 1942 at University of

Chicago
NOT the first nuclear reactor on Earth!
The Oklo Phenomenon
in the Oklo Uranium mine in Africa it is
observed that 235U levels are lower in those
parts where the total uranium content of
the rock is highest and fission product
elements are found in the deposits
o

o
o

when the rocks were formed 2 x 109

years ago 235U was 3% critical
mass
water in the clay mineral
moderated the neutrons
criticality was possibly maintained
for 106 years

Modern Nuclear Reactors

Fuel

Current nuclear reactors use UO2 fuel ~ less reactive than U metal
Enrichment is by fractional gaseous centrifugation of UF6 (easily
sublimed)
Breeder reactors generate new fuel during operation.
Neutron capture by 238U results in formation of 239Pu,
which is fissile. Significant amounts of Pu will only be
produced in an unmoderated reactor (fuel reprocessing
more dangerous!)

Cladding
Fuel container is usually stainless steel or zirconium alloy (resistance to
corrosion)
107

Moderators
Best moderators are light atoms;

H in water (so efficient at moderation that enriched fuel must be

used)
2
H in heavy water
10,11
B in boron-steel control rods,
12
C in graphite (must be highly purified)

Coolants

Water/Heavy Water ~ to keep it liquid it must be pressurized (PWR)

CO2 gas ~ in the Advanced Gas-Cooled Reactor (AGR)
Liquid-Na needed for the more severe cooling problems in breeder
reactors

Nuclear Fuel Reprocessing

Fission products 'poison' the fuel (by absorbing neutrons themselves) before
it is spent

'spent' fuel = uranium / plutonium / trans-uraniums (small

amounts) / ~30 fission products (inc. 2nd row transition metals /

lanthanides as alloys or complex oxide phases)
reprocessing exploits the different redox/complexation
chemistries of

uranium vs plutonium vs fission +

capture products

108

Organometallics

Organometallic chemistry of actinides is relatively recent

Similar to lanthanides in range of cyclopentadienides /
cyclooctatetraenides / alkyls
Cyclopentadienides are -bonded to actinides.
Compounds include:-

C5H5- does not behave ionically

but Cl is labile: formation of a wide variety of
(C5H5)3UX compounds
The most notable Cyclooctatetraenide is Uranocene

Green crystals
Paramagnetic
Pyrophoric
109

Stable to hydrolysis
Planar 'sandwich'
Eclipsed D8h conformation
UV-PES studies show that bonding in uranocene has 5f & 6d
contributions
o e2u symmetry interaction shown can only occur via f-orbitals

See: C. Elschenbroich & A. Salzer, Organometallics, 2nd ed.VCH, Weinheim, 1992

p. 363-5

Trans-Actinide Elements

Some atoms of elements 104 - 112 have probably been made

~ some are the subject of dispute:have they been made?
o who made them first?
o what should they be called?
They are assumed to comprise the start of a 4th Transition Series, but
chemical data is sketchy!
Any prospects for heavier elements?
o Plots of Half-life of Longest-Lived Isotope vs Z don't hold
out much hope!
o

Search for a "Magic Island"

Nuclear structure calculations possibly stable nuclei for Z ~
114
but no confirmed reports synthetically or in nature

110

LANTHANIDES &
ACTINIDES
Problems Set
1. Compare and contrast the chemistry of the lanthanides with those of the
first row transition metals and pre-transition metals.

2. Explain how you would prepare pure samples of the lanthanide elements,
and indicate how you would assess the purity of your samples.

3. (a) Explain why YbS and YbI2 are semiconducting solids, but LaS and
LaI2 show metallic behaviour.

(b) Compare and contrast the structures adopted by LaCl3, FeCl3 and AuCl3.

(c) Comment on the following statement: "Aqueous Eu2+ is

thermodynamically less susceptible to oxidation than any other aqueous M2+
lanthanide cations because of the stability of the half-filled 4f7 shell".

(d) Comment in the variation of the exothermic enthalpies of formation of

the lanthanide trichlorides, MCl3, given below (&endash;H in kJmol-1)
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb
1075 1058 1061 1045 1030 939.5 1012 1001 991 1009 1002 990 949

111

(e) Predict the magnetic moments you would expect for Pr3+ and Gd3+ salts.
Would you expect U4+ salts to have the same magnetic moments as Pr3+
salts?

4. Comment on points of interest in respect of the following compounds:(i) U(C8H8)2

(ii) (C5Me5)2LuMe
(iii) La1.85Sr0.15CuO4
(iv) Ce(NO3)63&endash;
(v) UO22+
(vi) Gd2Cl3
(vii) UF6

5. Traditionally uranium was assigned a place below tungsten as a 4th Row

transition element. In 1945 Seaborg re-assigned it as a member of the
Actinide 5f series. With this in mind, compare the chemistry of uranium
with those of tungsten and neodymium.

6. When sodium carbonate and uranium dioxide are heated in equimolar

proportions, at 800C under a flow of oxygen, a solid orange product A is
formed. The infra-red spectrum of A shows strong absorption bands near
900 cm-1, similar to those observed in aqueous solutions of uranyl salts.
When A is heated with a further equimolar quantity of UO2, a chocolate
brown compound B is obtained; B contains 77% uranium by weight. There
are no strong absorption bands near 900 cm-1 in the infra-red spectrum of B.
If UO2 and sodium carbonate are heated in 2:1 molar proportions under
oxygen at 800C, an orange compound C is formed. C is reduced by
hydrogen to compound B.
Describe the reactions involved in the above scheme.
Identify A, B and C.
112

[Atomic masses: U = 238, Na = 23, O = 16, C = 12]

7. (a) State how 238U92 can be converted into 239U94 and indicate which other
elements may be formed in the process. Suggest how these elements may be
separated from Pu.

(b) Suggest what happens in the following and, where possible, give
equations and comment on the species formed:

(i) Metallic plutonium dissolves in dilute HNO3.

(ii) The nature of the solid product (A) formed when HF is added to the
solution obtained in (i).

(iii) When A is heated with oxygen a mixture of two solids is obtained, B

and C. B is involatile and has the fluorite structure, whereas C is volatile
and has a relative molecular mass of 353. The IR and Raman spectra of
gaseous C have no band in common.

(iv) Hydrolysis of C results in the formation of a species D which has a

strong band at 710 cm-1 in its Raman spectrum.

(v) Reaction of C with two molar equivalents of CsF at 400 leads to

formation of a solid (E) and the evolution of 1 mol equivalent of fluorine
gas.

113