Lanthanide

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Lanthanides in the periodic table
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Helium
Lithium
Beryllium
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Carbon
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Iron
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Germanium
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Technetium
Ruthenium
Rhodium
Palladium
Silver
Cadmium
Indium
Tin
Antimony
Tellurium
Iodine
Xenon
Caesium
Barium
Lanthanum
Cerium
Praseodymium
Neodymium
Promethium
Samarium
Europium
Gadolinium
Terbium
Dysprosium
Holmium
Erbium
Thulium
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Osmium
Iridium
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Gold
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The lanthanide (/'l�n??na?d/) or lanthanoid (/'l�n??n??d/) series of chemical
elements[1] comprises the 15 metallic chemical elements with atomic numbers 57
through 71, from lanthanum through lutetium.[2][3][4] These elements, along with
the chemically similar elements scandium and yttrium, are often collectively known
as the rare earth elements.

The informal chemical symbol Ln is used in general discussions of lanthanide

chemistry to refer to any lanthanide. All but one of the lanthanides are f-block
elements, corresponding to the filling of the 4f electron shell; depending on the
source, either lanthanum or lutetium is considered a d-block element, but is
included due to its chemical similarities with the other 14.[5] All lanthanide
elements form trivalent cations, Ln3+, whose chemistry is largely determined by the
ionic radius, which decreases steadily from lanthanum to lutetium.

They are called lanthanides because the elements in the series are chemically
similar to lanthanum. Both lanthanum and lutetium have been labeled as group 3
elements, because they have a single valence electron in the 5d shell. However,
both elements are often included in discussions of the chemistry of lanthanide
elements. Lanthanum is the more often omitted of the two, because its placement as
a group 3 element is somewhat more common in texts and for semantic reasons: since
"lanthanide" means "like lanthanum", it has been argued that lanthanum cannot
logically be a lanthanide, but IUPAC acknowledges its inclusion based on common
usage.[6]

In presentations of the periodic table, the lanthanides and the actinides are
customarily shown as two additional rows below the main body of the table,[2] with
placeholders or else a selected single element of each series (either lanthanum and
actinium, or lutetium and lawrencium) shown in a single cell of the main table,
between barium and hafnium, and radium and rutherfordium, respectively. This
convention is entirely a matter of aesthetics and formatting practicality; a rarely
used wide-formatted periodic table inserts the lanthanide and actinide series in
their proper places, as parts of the table's sixth and seventh rows (periods).
The 1985 International Union of Pure and Applied Chemistry �Red Book� (p. 45)
recommends that "lanthanoid" is used rather than "lanthanide". The ending �-ide�
normally indicates a negative ion. However, owing to wide current use, �lanthanide�
is still allowed.

vte
Lanthanides
Lan�thanum
57
La
?138.91
Cerium
58
Ce
?140.12
Praseo�dymium
59
Pr
?140.91
Neo�dymium
60
Nd
?144.24
Prome�thium
61
Pm
?[145]
Sama�rium
62
Sm
?150.36
Europ�ium
63
Eu
?151.96
Gadolin�ium
64
Gd
?157.25
Ter�bium
65
Tb
?158.93
Dyspro�sium
66
Dy
?162.50
Hol�mium
67
Ho
?164.93
Erbium
68
Er
?167.26
Thulium
69
Tm
?168.93
Ytter�bium
70
Yb
?173.05
Lute�tium
71
Lu
?174.97
Primordial From decay Synthetic Border shows natural occurrence of the element

Contents
1 Etymology
2 Physical properties of the elements
3 Chemistry and compounds
3.1 Effect of 4f orbitals
3.2 Lanthanide oxidation states
3.3 Separation of lanthanides
3.4 Coordination chemistry and catalysis
3.4.1 Ln(III) compounds
3.4.2 Ln(II) and Ln(IV) compounds
3.4.3 Hydrides
3.4.4 Halides
3.4.5 Oxides and hydroxides
3.4.6 Chalcogenides (S, Se, Te)
3.4.7 Pnictides (group 15)
3.4.8 Carbides
3.4.9 Borides
3.4.10 Organometallic compounds
4 Physical properties
4.1 Magnetic and spectroscopic
5 Occurrence
6 Applications
6.1 Industrial
6.2 Life science
6.3 Upcoming Medical Uses
7 Biological effects
8 See also
9 References
10 Cited sources
11 External links
Etymology
Together with the two elements at the top of group 3, scandium and yttrium, the
trivial name "rare earths" is sometimes used to describe all the lanthanides; a
definition of rare earths including the group 3, lanthanide, and actinide elements
is also occasionally seen, and rarely Sc + Y + lanthanides + thorium.[citation
needed] The "earth" in the name "rare earths" arises from the minerals from which
they were isolated, which were uncommon oxide-type minerals. However, the use of
the name is deprecated by IUPAC, as the elements are neither rare in abundance nor
"earths" (an obsolete term for water-insoluble strongly basic oxides of
electropositive metals incapable of being smelted into metal using late 18th
century technology). Group 2 is known as the alkaline earth elements for much the
same reason.

The "rare" in the "rare earths" name has much more to do with the difficulty of
separating out each of the individual lanthanide elements than scarcity of any of
them. By way of the Greek "dysprositos" for "hard to get at," element 66,
dysprosium was similarly named; lanthanum itself is named after a word for
"hidden." The elements 57 (La) to 71 (Lu) are very similar chemically to one
another and frequently occur together in nature, often anywhere from three to all
15 of the lanthanides (along with yttrium as a 16th) occur in minerals such as
samarskite, monazite and many others which can also contain the other two group 3
elements as well as thorium and occasionally other actinides as well.[7] A majority
of the rare earths were discovered at the same mine in Ytterby, Sweden and four of
them are named (yttrium, ytterbium, erbium, terbium) after the city and a fifth
*(holmium) after Stockholm; scandium is named after Scandinavia, thulium after the
old name Thule, and the immediately-following group 4 element (number 72) hafnium
is named for the Latin name of the city of Copenhagen.[7]

Samarskite (a mineral which is the source of the name of the element samarium) and
other similar minerals in particular also have these elements in association with
the nearby metals tantalum, niobium, hafnium, zirconium, vanadium, and titanium,
from group 4 and group 5 often in similar oxidation states. Monazite is a phosphate
of numerous group 3 + lanthanide + actinide metals and mined especially for the
thorium content and specific rare earths especially lanthanum, yttrium and cerium.
Cerium and lanthanum as well as other members of the rare earth series are often
produced as a metal called mischmetal containing a variable mixture of these
elements with cerium and lanthanum predominating; it has direct uses such as
lighter flints and other spark sources which do not require extensive purification
of one of these metals.[7] There are also rare earth-bearing minerals based on
group 2 elements such as yttrocalcite, yttrocerite, yttrofluorite which vary in
content of yttrium, cerium, and lanthanum in a particular as well as varying
amounts of the others.[8] Other lanthanide/rare earth minerals include bastn�site,
florencite, chernovite, perovskite, xenotime, cerite, gadolinite, lanthanite,
fergusonite, polycrase, blomstrandine, h�leniusite, miserite, loparite,
lepersonnite, euxenite, all of which have a range of relative element concentration
and may have the symbol of a predominating one such as monazite-ce; group 3
elements do not occur as native element minerals in the fashion of gold, silver,
tantalum and many others on earth but may in lunar regolith. Very rare cerium,
lanthanum, and presumably other lanthanide/group 3 halides, feldspars and garnets
are also known to exist.[9]

All of this is the result of the order in which the electron shells of these
elements are filled -- the outermost has the same configuration for all of them,
and a deeper shell is progressively filled with electrons as the atomic number
increases from 57 towards 71.[7] For many years, mixtures of more than one rare
earth were considered to be single elements, such as neodymium and praseodymium
being thought to be the single element didymium and so on.[10] Very small
differences in solubility are used in solvent and ion-exchange purification methods
for these elements which require a great deal of repeating to get a purified metal.
The refined metals and their compounds have subtle and stark differences amongst
themselves in electronic, electrical, optical, and magnetic properties which
account for their many niche uses.[7]

By way of examples of the term meaning the above considerations rather than their
scarcity, cerium is the 26th most abundant element in the Earth's crust and more
abundant than copper,[7] neodymium is more abundant than gold; thulium (the second
least common naturally occurring lanthanide) is more abundant than iodine,[11]
which is itself common enough for biology to have evolved critical usages thereof,
and even the lone radioactive element in the series, promethium, is more common
than the two rarest naturally occurring elements, francium and astatine, combined.
Despite their abundance, even the technical term "lanthanides" could be interpreted
to reflect a sense of elusiveness on the part of these elements, as it comes from
the Greek ?a??a?e?? (lanthanein), "to lie hidden". However, if not referring to
their natural abundance, but rather to their property of "hiding" behind each other
in minerals, this interpretation is in fact appropriate. The etymology of the term
must be sought in the first discovery of lanthanum, at that time a so-called new
rare earth element "lying hidden" in a cerium mineral, and it is an irony that
lanthanum was later identified as the first in an entire series of chemically
similar elements and could give name to the whole series. The term "lanthanide" was
introduced by Victor Goldschmidt in 1925.[12]

Physical properties of the elements

Chemical element La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho
Er Tm Yb Lu
Atomic number 57 58 59 60 61 62 63 64 65 66 67
68 69 70 71
Image Lanthanum-2.jpg Cerium2.jpg Praseodymium.jpg Neodymium2.jpg
Samarium-2.jpg Europium.jpg Gadolinium-4.jpg Terbium-2.jpg Dy
chips.jpg Holmium2.jpg Erbium-crop.jpg Thulium sublimed dendritic and 1cm3
cube.jpg Ytterbium-3.jpg Lutetium sublimed dendritic and 1cm3 cube.jpg
Density (g/cm3) 6.162 6.770 6.77 7.01 7.26 7.52 5.244 7.90 8.23 8.540 8.79
9.066 9.32 6.90 9.841
Melting point (�C) 920 795 935 1024 1042 1072 826 1312 1356 1407
1461 1529 1545 824 1652
Boiling point (�C) 3464 3443 3520 3074 3000 1794 1529 3273 3230 2567
2720 2868 1950 1196 3402
Atomic electron configuration
(gas phase)* 5d1 4f15d1 4f3 4f4 4f5 4f6 4f7 4f75d1 4f9
4f10 4f11 4f12 4f13 4f14 4f145d1
Atomic electron configuration
(solid phase)* 5d1 4f15d1 4f25d1 4f35d1 4f45d1 4f55d1
4f7 4f75d1 4f85d1 4f95d1 4f105d1 4f115d1 4f125d1
4f14 4f145d1
Metal lattice (RT) dhcp fcc dhcp dhcp dhcp ** bcc hcp hcp hcp
hcp hcp hcp fcc hcp
Metallic radius (pm) 162 181.8 182.4 181.4 183.4 180.4 208.4 180.4 177.3 178.1
176.2 176.1 175.9 193.3 173.8
Resistivity at 25 �C (�O�cm) 57�80
20 �C 73 68 64 88 90 134 114 57 87 87 79 29
79
Magnetic susceptibility
?mol /10-6(cm3�mol-1) +95.9 +2500 (�) +5530(a) +5930 (a) +1278(a)
+30900 +185000
(350 K) +170000 (a) +98000 +72900 +48000 +24700 +67 (�)
+183
* Between initial Xe and final 6s2 electronic shells

** Sm has a close packed structure like the other lanthanides but has an unusual 9
layer repeat

Gschneider and Daane (1988) attribute the trend in melting point which increases
across the series, (lanthanum (920 �C) � lutetium (1622 �C)) to the extent of
hybridization of the 6s, 5d, and 4f orbitals. The hybridization is believed to be
at its greatest for cerium, which has the lowest melting point of all, 795 �C.[13]
The lanthanide metals are soft; their hardness increases across the series.[6]
Europium stands out, as it has the lowest density in the series at 5.24 g/cm3 and
the largest metallic radius in the series at 208.4 pm. It can be compared to
barium, which has a metallic radius of 222 pm. It is believed that the metal
contains the larger Eu2+ ion and that there are only two electrons in the
conduction band. Ytterbium also has a large metallic radius, and a similar
explanation is suggested.[6] The resistivities of the lanthanide metals are
relatively high, ranging from 29 to 134 �O�cm. These values can be compared to a
good conductor such as aluminium, which has a resistivity of 2.655 �O�cm. With the
exceptions of La, Yb, and Lu (which have no unpaired f electrons), the lanthanides
are strongly paramagnetic, and this is reflected in their magnetic
susceptibilities. Gadolinium becomes ferromagnetic at below 16 �C (Curie point).
The other heavier lanthanides � terbium, dysprosium, holmium, erbium, thulium, and
ytterbium � become ferromagnetic at much lower temperatures.[14]

Chemistry and compounds

Chemical element La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho
Er Tm Yb Lu
Atomic number 57 58 59 60 61 62 63 64 65 66 67
68 69 70 71
Ln3+ electron configuration*[15] 4f0 4f1 4f2 4f3 4f4 4f5 4f6 4f7
4f8 4f9 4f10 4f11 4f12 4f13
4f14

Ln3+ radius (pm)[6] 103 102 99 98.3 97 95.8 94.7 93.8 92.3 91.2
90.1 89 88 86.8 86.1
Ln4+ ion color in aqueous solution[16] � Orange-yellow Yellow Blue-
violet � � � � Red-brown Orange-yellow � � �
� �
Ln3+ ion color in aqueous solution[15] Colorless Colorless Green Violet
Pink Pale yellow Colorless Colorless V. pale pink Pale yellow Yellow
Rose Pale green Colorless Colorless
Ln2+ ion color in aqueous solution[6] � � � � � Blood red
Colorless � � � � � Violet-red Yellow-green �
* Not including initial [Xe] core

The colors of lanthanide complexes originate almost entirely from charge transfer
interactions between the metal and the ligand. f ? f transitions are symmetry
forbidden (or Laporte-forbidden), which is also true of transition metals. However,
transition metals are able to use vibronic coupling to break this rule. The valence
orbitals in lanthanides are almost entirely non-bonding and as such little
effective vibronic coupling takes, hence the spectra from f ? f transitions are
much weaker and narrower than those from d ? d transitions. In general this makes
the colors of lanthanide complexes far fainter than those of transition metal
complexes. f?f transitions are not possible for the f1 and f13 configurations of
Ce3+ and Yb3+ and thus these ions are colorless in aqueous solution.[17]

Approximate colors of lanthanide ions in aqueous solution[6][18][19]

Oxidation state 57 58 59 60 61 62 63 64 65 66 67
68 69 70 71
+2 Sm2+ Eu2+ Tm2+
Yb2+
+3 La3+ Ce3+ Pr3+ Nd3+ Pm3+ Sm3+ Eu3+ Gd3+ Tb3+ Dy3+ Ho3+ Er3+ Tm3+
Yb3+ Lu3+
+4 Ce4+ Pr4+ Nd4+ Tb4+ Dy4+

Effect of 4f orbitals
Going across the lanthanides in the periodic table, the 4f orbitals are usually
being filled. The effect of the 4f orbitals on the chemistry of the lanthanides is
profound and is the factor that distinguishes them from the transition metals.
There are seven 4f orbitals, and there are two different ways in which they are
depicted: as a "cubic set" or as a general set. The cubic set is fz3, fxz2, fyz2,
fxyz, fz(x2-y2), fx(x2-3y2) and fy(3x2-y2). The 4f orbitals penetrate the [Xe] core
and are isolated, and thus they do not participate in bonding. This explains why
crystal field effects are small and why they do not form p bonds.[15] As there are
seven 4f orbitals, the number of unpaired electrons can be as high as 7, which
gives rise to the large magnetic moments observed for lanthanide compounds.
Measuring the magnetic moment can be used to investigate the 4f electron
configuration, and this is a useful tool in providing an insight into the chemical
bonding.[20] The lanthanide contraction, i.e. the reduction in size of the Ln3+ ion
from La3+ (103 pm) to Lu3+ (86.1 pm), is often explained by the poor shielding of
the 5s and 5p electrons by the 4f electrons.[15]

Lanthanide oxides: clockwise from top center: praseodymium, cerium, lanthanum,

neodymium, samarium and gadolinium.
The electronic structure of the lanthanide elements, with minor exceptions, is
[Xe]6s24fn. The chemistry of the lanthanides is dominated by the +3 oxidation
state, and in LnIII compounds the 6s electrons and (usually) one 4f electron are
lost and the ions have the configuration [Xe]4fm.[21] All the lanthanide elements
exhibit the oxidation state +3. In addition, Ce3+ can lose its single f electron to
form Ce4+ with the stable electronic configuration of xenon. Also, Eu3+ can gain an
electron to form Eu2+ with the f7 configuration that has the extra stability of a
half-filled shell. Other than Ce(IV) and Eu(II), none of the lanthanides are stable
in oxidation states other than +3 in aqueous solution. Promethium is effectively a
man-made element, as all its isotopes are radioactive with half-lives shorter than
20 years.

In terms of reduction potentials, the Ln0/3+ couples are nearly the same for all
lanthanides, ranging from -1.99 (for Eu) to -2.35 V (for Pr). Thus these metals are
highly reducing, with reducing power similar to alkaline earth metals such as Mg (-
2.36 V).[6]

Lanthanide oxidation states

All of the lanthanide elements are commonly known to have the +3 oxidation state
and it was thought that only samarium, europium, and ytterbium had the +2 oxidation
readily accessible in solution. Now, it is known that all of the lanthanides can
form +2 complexes in solution.[22]
Ionization energies and reduction potentials of the elements
The ionization energies for the lanthanides can be compared with aluminium. In
aluminium the sum of the first three ionization energies is 5139 kJ�mol-1, whereas
the lanthanides fall in the range 3455 � 4186 kJ�mol-1. This correlates with the
highly reactive nature of the lanthanides.

The sum of the first two ionization energies for europium, 1632 kJ�mol-1 can be
compared with that of barium 1468.1 kJ�mol-1 and europium's third ionization energy
is the highest of the lanthanides. The sum of the first two ionization energies for
ytterbium are the second lowest in the series and its third ionization energy is
the second highest. The high third ionization energy for Eu and Yb correlate with
the half filling 4f7 and complete filling 4f14 of the 4f subshell, and the
stability afforded by such configurations due to exchange energy.[15] Europium and
ytterbium form salt like compounds with Eu2+ and Yb2+, for example the salt like
dihydrides.[23] Both europium and ytterbium dissolve in liquid ammonia forming
solutions of Ln2+(NH3)x again demonstrating their similarities to the alkaline
earth metals.[6]

The relative ease with which the 4th electron can be removed in cerium and (to a
lesser extent praseodymium) indicates why Ce(IV) and Pr(IV) compounds can be
formed, for example CeO2 is formed rather than Ce2O3 when cerium reacts with
oxygen.

Separation of lanthanides
The similarity in ionic radius between adjacent lanthanide elements makes it
difficult to separate them from each other in naturally occurring ores and other
mixtures. Historically, the very laborious processes of cascading and fractional
crystallization were used. Because the lanthanide ions have slightly different
radii, the lattice energy of their salts and hydration energies of the ions will be
slightly different, leading to a small difference in solubility. Salts of the
formula Ln(NO3)3�2NH4NO3�4H2O can be used. Industrially, the elements are separated
from each other by solvent extraction. Typically an aqueous solution of nitrates is
extracted into kerosene containing tri-n-butylphosphate. The strength of the
complexes formed increases as the ionic radius decreases, so solubility in the
organic phase increases. Complete separation can be achieved continuously by use of
countercurrent exchange methods. The elements can also be separated by ion-exchange
chromatography, making use of the fact that the stability constant for formation of
EDTA complexes increases for log K � 15.5 for [La(EDTA)]- to log K � 19.8 for
[Lu(EDTA)]-.[6][24]

Coordination chemistry and catalysis

When in the form of coordination complexes, lanthanides exist overwhelmingly in
their +3 oxidation state, although particularly stable 4f configurations can also
give +4 (Ce, Tb) or +2 (Eu, Yb) ions. All of these forms are strongly
electropositive and thus lanthanide ions are hard Lewis acids. The oxidation states
are also very stable; with the exceptions of SmI2[25] and cerium(IV) salts,[26]
lanthanides are not used for redox chemistry. 4f electrons have a high probability
of being found close to the nucleus and are thus strongly affected as the nuclear
charge increases across the series; this results in a corresponding decrease in
ionic radii referred to as the lanthanide contraction.

The low probability of the 4f electrons existing at the outer region of the atom or
ion permits little effective overlap between the orbitals of a lanthanide ion and
any binding ligand. Thus lanthanide complexes typically have little or no covalent
character and are not influenced by orbital geometries. The lack of orbital
interaction also means that varying the metal typically has little effect on the
complex (other than size), especially when compared to transition metals. Complexes
are held together by weaker electrostatic forces which are omni-directional and
thus the ligands alone dictate the symmetry and coordination of complexes. Steric
factors therefore dominate, with coordinative saturation of the metal being
balanced against inter-ligand repulsion. This results in a diverse range of
coordination geometries, many of which are irregular,[27] and also manifests itself
in the highly fluxional nature of the complexes. As there is no energetic reason to
be locked into a single geometry, rapid intramolecular and intermolecular ligand
exchange will take place. This typically results in complexes that rapidly
fluctuate between all possible configurations.

Many of these features make lanthanide complexes effective catalysts. Hard Lewis
acids are able to polarise bonds upon coordination and thus alter the
electrophilicity of compounds, with a classic example being the Luche reduction.
The large size of the ions coupled with their labile ionic bonding allows even
bulky coordinating species to bind and dissociate rapidly, resulting in very high
turnover rates; thus excellent yields can often be achieved with loadings of only a
few mol%.[28] The lack of orbital interactions combined with the lanthanide
contraction means that the lanthanides change in size across the series but that
their chemistry remains much the same. This allows for easy tuning of the steric
environments and examples exist where this has been used to improve the catalytic
activity of the complex[29][30][31] and change the nuclearity of metal clusters.
[32][33]

Despite this, the use of lanthanide coordination complexes as homogeneous catalysts

is largely restricted to the laboratory and there are currently few examples them
being used on an industrial scale.[34] It should be noted however, that lanthanides
exist in many forms other that coordination complexes and many of these are
industrially useful. In particular lanthanide metal oxides are used as
heterogeneous catalysts in various industrial processes.

Ln(III) compounds
The trivalent lanthanides mostly form ionic salts. The trivalent ions are hard
acceptors and form more stable complexes with oxygen-donor ligands than with
nitrogen-donor ligands. The larger ions are 9-coordinate in aqueous solution,
[Ln(H2O)9]3+ but the smaller ions are 8-coordinate, [Ln(H2O)8]3+. There is some
evidence that the later lanthanides have more water molecules in the second
coordination sphere.[35] Complexation with monodentate ligands is generally weak
because it is difficult to displace water molecules from the first coordination
sphere. Stronger complexes are formed with chelating ligands because of the chelate
effect, such as the tetra-anion derived from 1,4,7,10-tetraazacyclododecane-
1,4,7,10-tetraacetic acid (DOTA).

Samples of lanthanide nitrates in their hexahydrate form. From left to right: La,
Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
Ln(II) and Ln(IV) compounds
The most common divalent derivatives of the lanthanides are for Eu(II), which
achieves a favorable f7 configuration. Divalent halide derivatives are known for
all of the lanthanides. They are either conventional salts or are Ln(III)
"electride"-like salts. The simple salts include YbI2, EuI2, and SmI2. The
electride-like salts, described as Ln3+, 2I-, e-, include LaI2, CeI2 and GdI2. Many
of the iodides form soluble complexes with ethers, e.g. TmI2(dimethoxyethane)3.[36]
Samarium(II) iodide is a useful reducing agent. Ln(II) complexes can be synthesized
by transmetalation reactions. The normal range of oxidation states can be expanded
via the use of sterically bulky cyclopentadienyl ligands, in this way many
lanthanides can be isolated as Ln(II) compounds.[37]

Ce(IV) in ceric ammonium nitrate is a useful oxidizing agent. Otherwise tetravalent

lanthanides are rare. The Ce(IV) is the exception owing to the tendency to form an
unfilled f shell.

Hydrides
Chemical element La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho
Er Tm Yb Lu
Lanthanide metals react exothermically with hydrogen to form LnH2, dihydrides.[23]
With the exception of Eu and Yb which resemble the Ba and Ca hydrides (non
conducting, transparent salt like compounds) they form black pyrophoric, conducting
compounds[42] where the metal sub-lattice is face centred cubic and the H atoms
occupy tetrahedral sites.[23] Further hydrogenation produces a trihydride which is
non-stoichiometric, non-conducting, more salt like. The formation of trihydride is
associated with and increase in 8�10% volume and this is linked to greater
localization of charge on the hydrogen atoms which become more anionic (H- hydride
anion) in character.[23]

Halides
Lanthanide halides[6][43][44][42]
The only tetrahalides known are the tetrafluorides of cerium, praseodymium,
terbium, neodymium and dysprosium, the last two known only under matrix isolation
conditions.[6][47] All of the lanthanides form trihalides with fluorine, chlorine,
bromine and iodine. They are all high melting and predominantly ionic in nature.[6]
The fluorides are only slightly soluble in water and are not sensitive to air, and
this contrasts with the other halides which are air sensitive, readily soluble in
water and react at high temperature to form oxohalides.[48] The trihalides were
important as pure metal can be prepared from them.[6] In the gas phase the
trihalides are planar or approximately planar, the lighter lanthanides have a lower
% of dimers, the heavier lanthanides a higher proportion. The dimers have a similar
structure to Al2Cl6.[49]

Some of the dihalides are conducting while the rest are insulators. The conducting
forms can be considered as LnIII electride compounds where the electron is
delocalised into a conduction band, Ln3+ (X-)2(e-). All of the diodides have
relatively short metal-metal separations.[43] The CuTi2 structure of the lanthanum,
cerium and praseodymium diodides along with HP-NdI2 contain 44 nets of metal and
iodine atoms with short metal-metal bonds (393-386 La-Pr).[43] these compounds
should be considered to be two-dimensional metals (two-dimensional in the same way
that graphite is). The salt-like dihalides include those of Eu, Dy, Tm, and Yb. The
formation of a relatively stable +2 oxidation state for Eu and Yb is usually
explained by the stability (exchange energy) of half filled (f7) and fully filled
f14. GdI2 possesses the layered MoS2 structure, is ferromagnetic and exhibits
colossal magnetoresistance[43] The sesquihalides Ln2X3 and the Ln7I12 compounds
listed in the table contain metal clusters, discrete Ln6I12 clusters in Ln7I12 and
condensed clusters forming chains in the sesquihalides. Scandium forms a similar
cluster compound with chlorine, Sc7Cl12[6] Unlike many transition metal clusters
these lanthanide clusters do not have strong metal-metal interactions and this is
due to the low number of valence electrons involved, but instead are stabilised by
the surrounding halogen atoms.[43]

LaI is the only known monohalide. Prepared from the reaction of LaI3 and La metal,
it has a NiAs type structure and can be formulated La3+ (I-)(e-)2.[46]

Oxides and hydroxides

All of the lanthanides form sesquioxides, Ln2O3. The lighter/larger lanthanides
adopt a hexagonal 7-coordinate structure while the heavier/smaller ones adopt a
cubic 6-coordinate "C-M2O3" structure.[44] All of the sesquioxides are basic, and
absorb water and carbon dioxide from air to form carbonates, hydroxides and
hydroxycarbonates.[50] They dissolve in acids to form salts.[15]

Cerium forms a stoichiometric dioxide, CeO2, where cerium has an oxidation state of
+4. CeO2 is basic and dissolves with difficulty in acid to form Ce4+ solutions,
from which CeIV salts can be isolated, for example the hydrated nitrate
Ce(NO3)4.5H2O. CeO2 is used as an oxidation catalyst in catalytic converters.[15]
Praseodymium and terbium form non-stoichiometric oxides containing LnIV,[15]
although more extreme reaction conditions can produce stoichiometric (or near
stoichiometric) PrO2 and TbO2.[6]

Europium and ytterbium form salt-like monoxides, EuO and YbO, which have a rock
salt structure.[15] EuO is ferromagnetic at low temperatures,[6] and is a
semiconductor with possible applications in spintronics.[51] A mixed EuII/EuIII
oxide Eu3O4 can be produced by reducing Eu2O3 in a stream of hydrogen.[50]
Neodymium and samarium also form monoxides, but these are shiny conducting solids,
[6] although the existence of samarium monoxide is considered dubious.[50]

All of the lanthanides form hydroxides, Ln(OH)3. With the exception of lutetium
hydroxide, which has a cubic structure, they have the hexagonal UCl3 structure.[50]
The hydroxides can be precipitated from solutions of LnIII.[15] They can also be
formed by the reaction of the sesquioxide, Ln2O3, with water, but although this
reaction is thermodynamically favorable it is kinetically slow for the heavier
members of the series.[50] Fajans' rules indicate that the smaller Ln3+ ions will
be more polarizing and their salts correspondingly less ionic. The hydroxides of
the heavier lanthanides become less basic, for example Yb(OH)3 and Lu(OH)3 are
still basic hydroxides but will dissolve in hot concentrated NaOH.[6]

Chalcogenides (S, Se, Te)

All of the lanthanides form Ln2Q3 (Q= S, Se, Te).[15] The sesquisulfides can be
produced by reaction of the elements or (with the exception of Eu2S3) sulfidizing
the oxide (Ln2O3) with H2S.[15] The sesquisulfides, Ln2S3 generally lose sulfur
when heated and can form a range of compositions between Ln2S3 and Ln3S4. The
sesquisulfides are insulators but some of the Ln3S4 are metallic conductors (e.g.
Ce3S4) formulated (Ln3+)3 (S2-)4 (e-), while others (e.g. Eu3S4 and Sm3S4) are
semiconductors.[15] Structurally the sesquisulfides adopt structures that vary
according to the size of the Ln metal. The lighter and larger lanthanides favoring
7-coordinate metal atoms, the heaviest and smallest lanthanides (Yb and Lu)
favoring 6 coordination and the rest structures with a mixture of 6 and 7
coordination.[15] Polymorphism is common amongst the sesquisulfides.[52] The colors
of the sesquisulfides vary metal to metal and depend on the polymorphic form. The
colors of the ?-sesquisulfides are La2S3, white/yellow; Ce2S3, dark red; Pr2S3,
green; Nd2S3, light green; Gd2S3, sand; Tb2S3, light yellow and Dy2S3, orange.[53]
The shade of ?-Ce2S3 can be varied by doping with Na or Ca with hues ranging from
dark red to yellow,[43][53] and Ce2S3 based pigments are used commercially and are
seen as low toxicity substitutes for cadmium based pigments.[53]

All of the lanthanides form monochalcogenides, LnQ, (Q= S, Se, Te).[15] The
majority of the monochalcogenides are conducting, indicating a formulation LnIIIQ2-
(e-) where the electron is in conduction bands. The exceptions are SmQ, EuQ and YbQ
which are semiconductors or insulators but exhibit a pressure induced transition to
a conducting state.[52] Compounds LnQ2 are known but these do not contain LnIV but
are LnIII compounds containing polychalcogenide anions.[54]

Oxysulfides Ln2O2S are well known, they all have the same structure with 7-
coordinate Ln atoms, and 3 sulfur and 4 oxygen atoms as near neighbours.[55] Doping
these with other lanthanide elements produces phosphors. As an example, gadolinium
oxysulfide, Gd2O2S doped with Tb3+ produces visible photons when irradiated with
high energy X-rays and is used as a scintillator in flat panel detectors.[56] When
mischmetal, an alloy of lanthanide metals, is added to molten steel to remove
oxygen and sulfur, stable oxysulfides are produced that form an immiscible solid.
[15]

Pnictides (group 15)

All of the lanthanides form a mononitride, LnN, with the rock salt structure. The
mononitrides have attracted interest because of their unusual physical properties.
SmN and EuN are reported as being "half metals".[43] NdN, GdN, TbN and DyN are
ferromagnetic, SmN is antiferromagnetic.[57] Applications in the field of
spintronics are being investigated.[51] CeN is unusual as it is a metallic
conductor, contrasting with the other nitrides also with the other cerium
pnictides. A simple description is Ce4+N3- (e�) but the interatomic distances are a
better match for the trivalent state rather than for the tetravalent state. A
number of different explanations have been offered.[58] The nitrides can be
prepared by the reaction of lanthanum metals with nitrogen. Some nitride is
produced along with the oxide, when lanthanum metals are ignited in air.[15]
Alternative methods of synthesis are a high temperature reaction of lanthanide
metals with ammonia or the decomposition of lanthanide amides, Ln(NH2)3. Achieving
pure stoichiometric compounds, and crystals with low defect density has proved
difficult.[51] The lanthanide nitrides are sensitive to air and hydrolyse producing
ammonia.[42]

The other pnictides phosphorus, arsenic, antimony and bismuth also react with the
lanthanide metals to form monopnictides, LnQ. Additionally a range of other
compounds can be produced with varying stoichiometries, such as LnP2, LnP5, LnP7,
Ln3As, Ln5As3 and LnAs2.[59]

Carbides
Carbides of varying stoichiometries are known for the lanthanides. Non-
stoichiometry is common. All of the lanthanides form LnC2 and Ln2C3 which both
contain C2 units. The dicarbides with exception of EuC2, are metallic conductors
with the calcium carbide structure and can be formulated as Ln3+C22-(e�). The C-C
bond length is longer than that in CaC2, which contains the C22- anion, indicating
that the antibonding orbitals of the C22- anion are involved in the conduction
band. These dicarbides hydrolyse to form hydrogen and a mixture of hydrocarbons.
[60] EuC2 and to a lesser extent YbC2 hydrolyse differently producing a higher
percentage of acetylene (ethyne).[61] The sesquicarbides, Ln2C3 can be formulated
as Ln4(C2)3. These compounds adopt the Pu2C3 structure[43] which has been described
as having C22- anions in bisphenoid holes formed by eight near Ln neighbours.[62]
The lengthening of the C-C bond is less marked in the sesquicarbides than in the
dicarbides, with the exception of Ce2C3.[60] Other carbon rich stoichiometries are
known for some lanthanides. Ln3C4 (Ho-Lu) containing C, C2 and C3 units;[63] Ln4C7
(Ho-Lu) contain C atoms and C3 units[64] and Ln4C5 (Gd-Ho) containing C and C2
units.[65] Metal rich carbides contain interstitial C atoms and no C2 or C3 units.
These are Ln4C3 (Tb and Lu); Ln2C (Dy, Ho, Tm)[66][67] and Ln3C[43] (Sm-Lu).

Borides
All of the lanthanides form a number of borides. The "higher" borides (LnBx where x
> 12) are insulators/semiconductors whereas the lower borides are typically
conducting. The lower borides have stoichiometries of LnB2, LnB4, LnB6 and LnB12.
[68] Applications in the field of spintronics are being investigated.[51] The range
of borides formed by the lanthanides can be compared to those formed by the
transition metals. The boron rich borides are typical of the lanthanides (and
groups 1�3) whereas for the transition metals tend to form metal rich, "lower"
borides.[69] The lanthanide borides are typically grouped together with the group 3
metals with which they share many similarities of reactivity, stoichiometry and
structure. Collectively these are then termed the rare earth borides.[68]

Many methods of producing lanthanide borides have been used, amongst them are
direct reaction of the elements; the reduction of Ln2O3 with boron; reduction of
boron oxide, B2O3, and Ln2O3 together with carbon; reduction of metal oxide with
boron carbide, B4C.[68][69][70][71] Producing high purity samples has proved to be
difficult.[71] Single crystals of the higher borides have been grown in a low
melting metal (e.g. Sn, Cu, Al).[68]

Diborides, LnB2, have been reported for Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. All
have the same, AlB2, structure containing a graphitic layer of boron atoms. Low
temperature ferromagnetic transitions for Tb, Dy, Ho and Er. TmB2 is ferromagnetic
at 7.2 K.[43]

Tetraborides, LnB4 have been reported for all of the lanthanides except EuB4, all
have the same UB4 structure. The structure has a boron sub-lattice consists of
chains of octahedral B6 clusters linked by boron atoms. The unit cell decreases in
size successively from LaB4 to LuB4. The tetraborides of the lighter lanthanides
melt with decomposition to LnB6.[71] Attempts to make EuB4 have failed.[70] The
LnB4 are good conductors[68] and typically antiferromagnetic.[43]

Hexaborides, LnB6 have been reported for all of the lanthanides. They all have the
CaB6 structure, containing B6 clusters. They are non-stoichiometric due to cation
defects. The hexaborides of the lighter lanthanides (La � Sm) melt without
decomposition, EuB6 decomposes to boron and metal and the heavier lanthanides
decompose to LnB4 with exception of YbB6 which decomposes forming YbB12. The
stability has in part been correlated to differences in volatility between the
lanthanide metals.[71] In EuB6 and YbB6 the metals have an oxidation state of +2
whereas in the rest of the lanthanide hexaborides it is +3. This rationalises the
differences in conductivity, the extra electrons in the LnIII hexaborides entering
conduction bands. EuB6 is a semiconductor and the rest are good conductors.[43][71]
LaB6 and CeB6 are thermionic emitters, used, for example, in scanning electron
microscopes.[72]

Dodecaborides, LnB12, are formed by the heavier smaller lanthanides, but not by the
lighter larger metals, La � Eu. With the exception YbB12 (where Yb takes an
intermediate valence and is a Kondo insulator), the dodecaborides are all metallic
compounds. They all have the UB12 structure containing a 3 dimensional framework of
cubooctahedral B12 clusters.[68]
The higher boride LnB66 is known for all lanthanide metals. The composition is
approximate as the compounds are non-stoichiometric.[68] They all have similar
complex structure with over 1600 atoms in the unit cell. The boron cubic sub
lattice contains super icosahedra made up of a central B12 icosahedra surrounded by
12 others, B12(B12)12.[68] Other complex higher borides LnB50 (Tb, Dy, Ho Er Tm Lu)
and LnB25 are known (Gd, Tb, Dy, Ho, Er) and these contain boron icosahedra in the
boron framework.[68]

Organometallic compounds
Lanthanide-carbon s bonds are well known; however as the 4f electrons have a low
probability of existing at the outer region of the atom there is little effective
orbital overlap, resulting in bonds with significant ionic character. As such
organo-lanthanide compounds exhibit carbanion-like behavior, unlike the behavior in
transition metal organometallic compounds. Because of their large size, lanthanides
tend to form more stable organometallic derivatives with bulky ligands to give
compounds such as Ln[CH(SiMe3)3].[73] Analogues of uranocene are derived from
dilithiocyclooctatetraene, Li2C8H8. Organic lanthanide(II) compounds are also
known, such as Cp*2Eu.[36]

Physical properties
Magnetic and spectroscopic
All the trivalent lanthanide ions, except lanthanum and lutetium, have unpaired f
electrons. However, the magnetic moments deviate considerably from the spin-only
values because of strong spin-orbit coupling. The maximum number of unpaired
electrons is 7, in Gd3+, with a magnetic moment of 7.94 B.M., but the largest
magnetic moments, at 10.4�10.7 B.M., are exhibited by Dy3+ and Ho3+. However, in
Gd3+ all the electrons have parallel spin and this property is important for the
use of gadolinium complexes as contrast reagent in MRI scans.

A solution of 4% holmium oxide in 10% perchloric acid, permanently fused into a

quartz cuvette as a wavelength calibration standard
Crystal field splitting is rather small for the lanthanide ions and is less
important than spin-orbit coupling in regard to energy levels.[6] Transitions of
electrons between f orbitals are forbidden by the Laporte rule. Furthermore,
because of the "buried" nature of the f orbitals, coupling with molecular
vibrations is weak. Consequently, the spectra of lanthanide ions are rather weak
and the absorption bands are similarly narrow. Glass containing holmium oxide and
holmium oxide solutions (usually in perchloric acid) have sharp optical absorption
peaks in the spectral range 200�900 nm and can be used as a wavelength calibration
standard for optical spectrophotometers,[74] and are available commercially.[75]

As f-f transitions are Laporte-forbidden, once an electron has been excited, decay
to the ground state will be slow. This makes them suitable for use in lasers as it
makes the population inversion easy to achieve. The Nd:YAG laser is one that is
widely used. Europium-doped yttrium vanadate was the first red phosphor to enable
the development of color television screens.[76] Lanthanide ions have notable
luminescent properties due to their unique 4f orbitals. Laporte forbidden f-f
transitions can be activated by excitation of a bound "antenna" ligand. This leads
to sharp emission bands throughout the visible, NIR, and IR and relatively long
luminescence lifetimes.[77]

Occurrence
Main article: Rare earth element � Geological distribution
The lanthanide contraction is responsible for the great geochemical divide that
splits the lanthanides into light and heavy-lanthanide enriched minerals, the
latter being almost inevitably associated with and dominated by yttrium. This
divide is reflected in the first two "rare earths" that were discovered: yttria
(1794) and ceria (1803). The geochemical divide has put more of the light
lanthanides in the Earth's crust, but more of the heavy members in the Earth's
mantle. The result is that although large rich ore-bodies are found that are
enriched in the light lanthanides, correspondingly large ore-bodies for the heavy
members are few. The principal ores are monazite and bastn�site. Monazite sands
usually contain all the lanthanide elements, but the heavier elements are lacking
in bastn�site. The lanthanides obey the Oddo-Harkins rule � odd-numbered elements
are less abundant than their even-numbered neighbors.

Three of the lanthanide elements have radioactive isotopes with long half-lives
(138La, 147Sm and 176Lu) that can be used to date minerals and rocks from Earth,
the Moon and meteorites.[78]

Applications
Industrial
Lanthanide elements and their compounds have many uses but the quantities consumed
are relatively small in comparison to other elements. About 15000 ton/year of the
lanthanides are consumed as catalysts and in the production of glasses. This 15000
tons corresponds to about 85% of the lanthanide production. From the perspective of
value, however, applications in phosphors and magnets are more important.[79]

The devices lanthanide elements are used in include superconductors, samarium-

cobalt and neodymium-iron-boron high-flux rare-earth magnets, magnesium alloys,
electronic polishers, refining catalysts and hybrid car components (primarily
batteries and magnets).[80] Lanthanide ions are used as the active ions in
luminescent materials used in optoelectronics applications, most notably the Nd:YAG
laser. Erbium-doped fiber amplifiers are significant devices in optical-fiber
communication systems. Phosphors with lanthanide dopants are also widely used in
cathode ray tube technology such as television sets. The earliest color television
CRTs had a poor-quality red; europium as a phosphor dopant made good red phosphors
possible. Yttrium iron garnet (YIG) spheres can act as tunable microwave
resonators. Lanthanide oxides are mixed with tungsten to improve their high
temperature properties for TIG welding, replacing thorium, which was mildly
hazardous to work with. Many defense-related products also use lanthanide elements
such as night vision goggles and rangefinders. The SPY-1 radar used in some Aegis
equipped warships, and the hybrid propulsion system of Arleigh Burke-class
destroyers all use rare earth magnets in critical capacities.[81] The price for
lanthanum oxide used in fluid catalytic cracking has risen from $5 per kilogram in
early 2010 to $140 per kilogram in June 2011.[82]

Most lanthanides are widely used in lasers, and as (co-)dopants in doped-fiber

optical amplifiers; for example, in Er-doped fiber amplifiers, which are used as
repeaters in the terrestrial and submarine fiber-optic transmission links that
carry internet traffic. These elements deflect ultraviolet and infrared radiation
and are commonly used in the production of sunglass lenses. Other applications are
summarized in the following table:[11]

Application Percentage
Catalytic converters 45
Petroleum refining catalysts 25
Permanent magnets 12
Glass polishing and ceramics 7
Metallurgical 7
Phosphors 3
Other 1
The complex Gd(DOTA) is used in magnetic resonance imaging.

Life science
As mentioned in the industrial applications section above, lanthanide metals are
particularly useful in technologies that take advantage of their reactivity to
specific wavelengths of light.[83] Certain life science applications take advantage
of the unique luminescence properties of lanthanide ion complexes (Ln(III) chelates
or cryptates). These are well-suited for this application due to their large Stokes
shifts and extremely long emission lifetimes (from microseconds to milliseconds)
compared to more traditional fluorophores (e.g., fluorescein, allophycocyanin,
phycoerythrin, and rhodamine). The biological fluids or serum commonly used in
these research applications contain many compounds and proteins which are naturally
fluorescent. Therefore, the use of conventional, steady-state fluorescence
measurement presents serious limitations in assay sensitivity. Long-lived
fluorophores, such as lanthanides, combined with time-resolved detection (a delay
between excitation and emission detection) minimizes prompt fluorescence
interference.

Time-resolved fluorometry (TRF) combined with fluorescence resonance energy

transfer (FRET) offers a powerful tool for drug discovery researchers: Time-
Resolved Fluorescence Resonance Energy Transfer or TR-FRET. TR-FRET combines the
low background aspect of TRF with the homogeneous assay format of FRET. The
resulting assay provides an increase in flexibility, reliability and sensitivity in
addition to higher throughput and fewer false positive/false negative results.

This method involves two fluorophores: a donor and an acceptor. Excitation of the
donor fluorophore (in this case, the lanthanide ion complex) by an energy source
(e.g. flash lamp or laser) produces an energy transfer to the acceptor fluorophore
if they are within a given proximity to each other (known as the F�rster�s radius).
The acceptor fluorophore in turn emits light at its characteristic wavelength.

The two most commonly used lanthanides in life science assays are shown below along
with their corresponding acceptor dye as well as their excitation and emission
wavelengths and resultant Stokes shift (separation of excitation and emission
wavelengths).

Donor Excitation?Emission ? (nm) Acceptor Excitation?Emission ? (nm)

Stoke's Shift (nm)
Eu3+ 340?615 Allophycocyanin 615?660 320
Tb3+ 340?545 Phycoerythrin 545?575 235
Upcoming Medical Uses
Currently there is research showing that lanthanides elements can be used as
anticancer agents. The main role of the lanthanides in these studies is to inhibit
proliferation of the cancer cells. Specifically cerium and lanthanum have been
studied for their role as anti-cancer agents.

One of the specific elements from the lanthanide group that has been tested and
used is cerium (Ce). There have been studies that use a protein-cerium complex to
observe the effect of cerium on the cancer cells. The hope was to inhibit cell
proliferation and promote cytotoxicity.[84] Transferrin receptors in cancer cells,
such as those in breast cancer cells and epithelial cervical cells, promote the
cell proliferation and malignancy of the cancer.[84] Transferrin is a protein used
to transport iron into the cells and is needed to aid the cancer cells in DNA
replication. Transferrin acts as a growth factor for the cancerous cells and is
dependent on iron. Cancer cells have much higher levels of transferrin receptors
than normal cells and are very dependent on iron for their proliferation.[84]
Cerium has shown results as an anti-cancer agent due to its similarities in
structure and biochemistry to iron. Cerium may bind in the place of iron on to the
transferrin and then be brought into the cancer cells by transferrin-receptor
mediated endocytosis.[84] The cerium binding to the transferrin in place of the
iron inhibits the transferrin activity in the cell. This creates a toxic
environment for the cancer cells and causes a decrease in cell growth. This is the
proposed mechanism for cerium�s effect on cancer cells, though the real mechanism
may be more complex in how cerium inhibits cancer cell proliferation. Specifically
in HeLa cancer cells studied in vitro, cell viability was decreased after 48 to 72
hours of cerium treatments. Cells treated with just cerium had decreases in cell
viability, but cells treated with both cerium and transferrin had more significant
inhibition for cellular activity.[84]

Another specific element that has been tested and used as an anti-cancer agent is
lanthanum, more specifically lanthanum chloride (LaCl3 ). The lanthanum ion is used
to affect the levels of let-7a and microRNAs miR-34a in a cell throughout the cell
cycle. When the lanthanum ion was introduced to the cell in vivo or in vitro, it
inhibited the rapid growth and induced apoptosis of the cancer cells (specifically
cervical cancer cells). This effect was caused by the regulation of the let-7a and
microRNAs by the lanthanum ions.[85] The mechanism for this effect is still unclear
but it is possible that the lanthanum is acting in a similar way as the cerium and
binding to a ligand necessary for cancer cell proliferation.

Biological effects
Due to their sparse distribution in the earth's crust and low aqueous solubility,
the lanthanides have a low availability in the biosphere, and for a long time were
not known to naturally form part of any biological molecules. In 2007 a novel
methanol dehydrogenase that strictly uses lanthanides as enzymatic cofactors was
discovered in a bacterium from the phylum Verrucomicrobia, Methylacidiphilum
fumariolicum. This bacterium was found to survive only if there are lanthanides
present in the environment.[86] Compared to most other nondietary elements, non-
radioactive lanthanides are classified as having low toxicity.[79]

See also
Actinide
Group 3 element
Lanthanide contraction
Rare earth element
Lanthanide probes
References
The current IUPAC recommendation is that the name lanthanoid be used rather than
lanthanide, as the suffix "-ide" is preferred for negative ions, whereas the suffix
"-oid" indicates similarity to one of the members of the containing family of
elements. However, lanthanide is still favored in most (~90%) scientific
articles[citation needed] and is currently adopted on Wikipedia. In the older
literature, the name "lanthanon" was often used.
Gray, Theodore (2009). The Elements: A Visual Exploration of Every Known Atom in
the Universe. New York: Black Dog & Leventhal Publishers. p. 240. ISBN 978-1-57912-
814-2.
Lanthanide Archived 2011-09-11 at the Wayback Machine, Encyclop�dia Britannica on-
line
Holden, Norman E.; Coplen, Tyler (January�February 2004). "The Periodic Table of
the Elements". Chemistry International. 26 (1): 8. doi:10.1515/ci.2004.26.1.8.
Archived from the original on 2004-02-17. Retrieved 23 March 2010.
F Block Elements, Oxidation States, Lanthanides and Actinides.
Chemistry.tutorvista.com. Retrieved on 2017-12-14.
Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.).
Butterworth-Heinemann. pp. 1230�1242. ISBN 978-0-08-037941-8.
"The Elements", Theodore Gray, Black-Dog & Leventhal, Chicago 2007: "Lanthanum"
and "Cerium" entries Ch 57 & 58, pp 134-7
Rocks & Minerals, A Guide To Field Identification, Sorrell, St Martin's Press
1972, 1995, pp 118 (Halides), 228 (Carbonates)
Minearls of the World, Johnsen, 2000
"The Elements", Theodore Gray, Black Dog & Leventhal, Chicago 2007: "Neodymium"
and "Praseodymium" entries Ch 59 & 60, pp 138-43
Aspinall, Helen C. (2001). Chemistry of the f-block elements. CRC Press. p. 8.
ISBN 978-90-5699-333-7.
 Hakala, Reino W. (1952). "Letters". Journal of Chemical Education. 29 (11): 581.
Bibcode:1952JChEd..29..581H. doi:10.1021/ed029p581.2.
Krishnamurthy, Nagaiyar and Gupta, Chiranjib Kumar (2004) Extractive Metallurgy of
Rare Earths, CRC Press, ISBN 0-415-33340-7
Cullity, B. D. and Graham, C. D. (2011) Introduction to Magnetic Materials, John
Wiley & Sons, ISBN 9781118211496
Cotton, Simon (2006). Lanthanide and Actinide Chemistry. John Wiley & Sons Ltd.
Sroor, Farid M.A.; Edelmann, Frank T. (2012). "Lanthanides: Tetravalent
Inorganic". Encyclopedia of Inorganic and Bioinorganic Chemistry.
doi:10.1002/9781119951438.eibc2033. ISBN 9781119951438.
McGill, Ian, "Rare Earth Elements", Ullmann's Encyclopedia of Industrial
Chemistry, 31, Weinheim: Wiley-VCH, p. 191, doi:10.1002/14356007.a22_607
Holleman, p. 1937.
dtv-Atlas zur Chemie 1981, Vol. 1, p. 220.
Bochkarev, Mikhail N.; Fedushkin, Igor L.; Fagin, Anatoly A.; Petrovskaya, Tatyana
V.; Ziller, Joseph W.; Broomhall-Dillard, Randy N. R.; Evans, William J. (1997).
"Synthesis and Structure of the First Molecular Thulium(II) Complex:
[TmI2(MeOCH2CH2OMe)3]". Angewandte Chemie International Edition in English. 36
(12): 133�135. doi:10.1002/anie.199701331.
Winter, Mark. "Lanthanum ionisation energies". WebElements Ltd, UK. Retrieved
2010-09-02.
MacDonald, Matthew R.; Bates, Jefferson E.; Ziller, Joseph W.; Furche, Filipp;
Evans, William J. (3 July 2013). "Completing the Series of +2 Ions for the
Lanthanide Elements: Synthesis of Molecular Complexes of Pr, Gd, Tb, and Lu".
Journal of the American Chemical Society. 135 (26): 9857�9868.
doi:10.1021/ja403753j. PMID 23697603.
Fukai, Y. (2005). The Metal-Hydrogen System, Basic Bulk Properties, 2d edition.
Springer. ISBN 978-3-540-00494-3.
Pettit, L. and Powell, K. SC-database. Acadsoft.co.uk. Retrieved on 2012-01-15.
Molander, Gary A.; Harris, Christina R. (1 January 1996). "Sequencing Reactions
with Samarium(II) Iodide". Chemical Reviews. 96 (1): 307�338.
doi:10.1021/cr950019y. PMID 11848755.
Nair, Vijay; Balagopal, Lakshmi; Rajan, Roshini; Mathew, Jessy (1 January 2004).
"Recent Advances in Synthetic Transformations Mediated by Cerium(IV) Ammonium
Nitrate". Accounts of Chemical Research. 37 (1): 21�30. doi:10.1021/ar030002z. PMID
14730991.
Dehnicke, Kurt; =Greiner, Andreas (2003). "Unusual Complex Chemistry of Rare-Earth
Elements: Large Ionic Radii�Small Coordination Numbers". Angewandte Chemie
International Edition. 42 (12): 1340�1354. doi:10.1002/anie.200390346. PMID
12671966.
Aspinall, Helen C. (2001). Chemistry of the f-block elements. Amsterdam [u.a.]:
Gordon & Breach. ISBN 978-9056993337.
Kobayashi, Shu; Hamada, Tomoaki; Nagayama, Satoshi; Manabe, Kei (1 January 2001).
"Lanthanide Trifluoromethanesulfonate-Catalyzed Asymmetric Aldol Reactions in
Aqueous Media". Organic Letters. 3 (2): 165�167. doi:10.1021/ol006830z. PMID
11430025.
Aspinall, Helen C.; Dwyer, Jennifer L.; Greeves, Nicholas; Steiner, Alexander (1
April 1999). "Li3[Ln(binol)3]�6THF: New Anhydrous Lithium Lanthanide Binaphtholates
and Their Use in Enantioselective Alkyl Addition to Aldehydes". Organometallics. 18
(8): 1366�1368. doi:10.1021/om981011s.
Parac-Vogt, Tatjana N.; Pachini, Sophia; Nockemann, Peter; VanmHecke, Kristof; Van
Meervelt, Luc; Binnemans, Koen (1 November 2004). "Lanthanide(III)
Nitrobenzenesulfonates as New Nitration Catalysts: The Role of the Metal and of the
Counterion in the Catalytic Efficiency". European Journal of Organic Chemistry
(Submitted manuscript). 2004 (22): 4560�4566. doi:10.1002/ejoc.200400475.
Lipstman, Sophia; Muniappan, Sankar; George, Sumod; Goldberg, Israel (1 January
2007). "Framework coordination polymers of tetra(4-carboxyphenyl)porphyrin and
lanthanide ions in crystalline solids". Dalton Transactions (30): 3273�81.
doi:10.1039/B703698A. PMID 17893773.
 Bretonni�re, Yann; Mazzanti, Marinella; P�caut, Jacques; Dunand, Frank A.;
Merbach, Andr� E. (1 December 2001). "Solid-State and Solution Properties of the
Lanthanide Complexes of a New Heptadentate Tripodal Ligand: A Route to Gadolinium
Complexes with an Improved Relaxation Efficiency". Inorganic Chemistry. 40 (26):
6737�6745. doi:10.1021/ic010591. PMID 11735486.
Trinadhachari, Ganala Naga; Kamat, Anand Gopalkrishna; Prabahar, Koilpillai
Joseph; Handa, Vijay Kumar; Srinu, Kukunuri Naga Venkata Satya; Babu, Korupolu
Raghu; Sanasi, Paul Douglas (15 March 2013). "Commercial Scale Process of
Galanthamine Hydrobromide Involving Luche Reduction: Galanthamine Process Involving
Regioselective 1,2-Reduction of a,�-Unsaturated Ketone". Organic Process Research &
Development. 17 (3): 406�412. doi:10.1021/op300337y.
Burgess, J. (1978). Metal ions in solution. New York: Ellis Horwood. ISBN 978-0-
85312-027-8.
Nief, F. (2010). "Non-classical divalent lanthanide complexes". Dalton Trans. 39
(29): 6589�6598. doi:10.1039/c001280g. PMID 20631944.
Evans, William J. (15 September 2016). "Tutorial on the Role of Cyclopentadienyl
Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide
Metals in New Oxidation States". Organometallics. 35 (18): 3088�3100.
doi:10.1021/acs.organomet.6b00466.open access
Kohlmann, H.; Yvon, K. (2000). "The crystal structures of EuH2 and EuLiH3 by
neutron powder diffraction". Journal of Alloys and Compounds. 299 (1�2): L16�L20.
doi:10.1016/S0925-8388(99)00818-X.
Matsuoka, T.; Fujihisa, H.; Hirao, N.; Ohishi, Y.; Mitsui, T.; Masuda, R.; Seto,
M.; Yoda, Y.; Shimizu, K.; Machida, A.; Aoki, K. (2011). "Structural and Valence
Changes of Europium Hydride Induced by Application of High-Pressure H2". Physical
Review Letters. 107 (2): 025501. Bibcode:2011PhRvL.107b5501M.
doi:10.1103/PhysRevLett.107.025501. PMID 21797616.
Tellefsen, M.; Kaldis, E.; Jilek, E. (1985). "The phase diagram of the Ce-H2
system and the CeH2-CeH3 solid solutions". Journal of the Less Common Metals. 110
(1�2): 107�117. doi:10.1016/0022-5088(85)90311-X.
Kumar, Pushpendra; Philip, Rosen; Mor, G. K.; Malhotra, L. K. (2002). "Influence
of Palladium Overlayer on Switching Behaviour of Samarium Hydride Thin Films".
Japanese Journal of Applied Physics. 41 (Part 1, No. 10): 6023�6027.
Bibcode:2002JaJAP..41.6023K. doi:10.1143/JJAP.41.6023.
Holleman, p. 1942
David A. Atwood, ed. (19 February 2013). The Rare Earth Elements: Fundamentals and
Applications (eBook). John Wiley & Sons. ISBN 9781118632635.
Wells, A. F. (1984). Structural Inorganic Chemistry (5th ed.). Oxford Science
Publication. ISBN 978-0-19-855370-0.
Perry, Dale L. (2011). Handbook of Inorganic Compounds, Second Edition. Boca
Raton, Florida: CRC Press. p. 125. ISBN 978-1-43981462-8. Retrieved 2014-02-17.
Ryazanov, Mikhail; Kienle, Lorenz; Simon, Arndt; Mattausch, Hansj�rgen (2006).
"New Synthesis Route to and Physical Properties of Lanthanum Monoiodide�".
Inorganic Chemistry. 45 (5): 2068�2074. doi:10.1021/ic051834r. PMID 16499368.
Vent-Schmidt, T.; Fang, Z.; Lee, Z.; Dixon, D.; Riedel, S. (2016). "Extending the
Row of Lanthanide Tetrafluorides: A Combined Matrix-Isolation and Quantum-Chemical
Study". Chemistry. 22 (7): 2406�16. doi:10.1002/chem.201504182. PMID 26786900.
Haschke, John. M. (1979). "Chapter 32:Halides". In Gschneider Jr., K. A. (ed.).
Handbook on the Physics and Chemistry of Rare Earths vol 4. North Holland
Publishing Company. pp. 100�110. ISBN 978-0-444-85216-8.
Kov�cs, Attila (2004). "Structure and Vibrations of Lanthanide Trihalides: An
Assessment of Experimental and Theoretical Data". Journal of Physical and Chemical
Reference Data. 33 (1): 377. Bibcode:2004JPCRD..33..377K. doi:10.1063/1.1595651.
Adachi, G.; Imanaka, Nobuhito and Kang, Zhen Chuan (eds.) (2006) Binary Rare Earth
Oxides. Springer. ISBN 1-4020-2568-8
Nasirpouri, Farzad and Nogaret, Alain (eds.) (2011) Nanomagnetism and Spintronics:
Fabrication, Materials, Characterization and Applications. World Scientific. ISBN
9789814273053
Flahaut, Jean (1979). "Chapter 31:Sulfides, Selenides and Tellurides". In
Gschneider Jr., K. A. (ed.). Handbook on the Physics and Chemistry of Rare Earths
vol 4. North Holland Publishing Company. pp. 100�110. ISBN 978-0-444-85216-8.
Berte, Jean-Noel (2009). "Cerium pigments". In Smith, Hugh M. (ed.). High
Performance Pigments. Wiley-VCH. ISBN 978-3-527-30204-8.
Holleman, p. 1944.
Liu, Guokui and Jacquier, Bernard (eds) (2006) Spectroscopic Properties of Rare
Earths in Optical Materials, Springer
Sisniga, Alejandro (2012). "Chapter 15". In Iniewski, Krzysztof (ed.). Integrated
Microsystems: Electronics, Photonics, and Biotechnology. CRC Press. ISBN 978-3-527-
31405-8.
Temmerman, W. M. (2009). "Chapter 241: The Dual, Localized or Band-Like, Character
of the 4f-States". In Gschneider Jr., K. A. (ed.). Handbook on the Physics and
Chemistry of Rare Earths vol 39. Elsevier. pp. 100�110. ISBN 978-0-444-53221-3.
Dronskowski, R. (2005) Computational Chemistry of Solid State Materials: A Guide
for Materials Scientists, Chemists, Physicists and Others, Wiley, ISBN
9783527314102
Hulliger, F. (1979). "Chapter 33: Rare Earth Pnictides". In Gschneider Jr., K. A.
(ed.). Handbook on the Physics and Chemistry of Rare Earths vol 4. North Holland
Publishing Company. pp. 100�110. ISBN 978-0-444-85216-8.
Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.).
Butterworth-Heinemann. pp. 297�299. ISBN 978-0-08-037941-8.
Spedding, F. H.; Gschneidner, K.; Daane, A. H. (1958). "The Crystal Structures of
Some of the Rare Earth Carbides". Journal of the American Chemical Society. 80
(17): 4499�4503. doi:10.1021/ja01550a017.
Wang, X.; Loa, I.; Syassen, K.; Kremer, R.; Simon, A.; Hanfland, M.; Ahn, K.
(2005). "Structural properties of the sesquicarbide superconductor La2C3 at high
pressure". Physical Review B. 72 (6): 064520. arXiv:cond-mat/0503597.
Bibcode:2005PhRvB..72f4520W. doi:10.1103/PhysRevB.72.064520.
Poettgen, Rainer.; Jeitschko, Wolfgang. (1991). "Scandium carbide, Sc3C4, a
carbide with C3 units derived from propadiene". Inorganic Chemistry. 30 (3):
427�431. doi:10.1021/ic00003a013.
Czekalla, Ralf; Jeitschko, Wolfgang; Hoffmann, Rolf-Dieter; Rabeneck, Helmut
(1996). "Preparation, Crystal Structure, and Properties of the Lanthanoid Carbides
Ln4C7 with Ln: Ho, Er, Tm, and Lu" (PDF). Z. Naturforsch. B. 51 (5): 646�654.
doi:10.1515/znb-1996-0505.
Czekalla, Ralf; H�fken, Thomas; Jeitschko, Wolfgang; Hoffmann, Rolf-Dieter;
P�ttgen, Rainer (1997). "The Rare Earth Carbides R4C5 with R=Y, Gd, Tb, Dy, and
Ho". Journal of Solid State Chemistry. 132 (2): 294�299.
Bibcode:1997JSSCh.132..294C. doi:10.1006/jssc.1997.7461.
Atoji, Masao (1981). "Neutron-diffraction study of Ho2C at 4�296 K". The Journal
of Chemical Physics. 74 (3): 1893. Bibcode:1981JChPh..74.1893A.
doi:10.1063/1.441280.
Atoji, Masao (1981). "Neutron-diffraction studies of Tb2C and Dy2C in the
temperature range 4�296 K". The Journal of Chemical Physics. 75 (3): 1434.
Bibcode:1981JChPh..75.1434A. doi:10.1063/1.442150.
Mori, Takao (2008). "Chapter 238:Higher Borides". In Gschneider Jr., K. A. (ed.).
Handbook on the Physics and Chemistry of Rare Earths vol 38. North Holland. pp.
105�174. ISBN 978-0-444-521439.
Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.).
Butterworth-Heinemann. p. 147. ISBN 978-0-08-037941-8.
Refractory Materials, Volume 6-IV: 1976, ed. Allen Alper, Elsevier, ISBN 0-12-
053204-2
Zuckerman, J. J. (2009) Inorganic Reactions and Methods, The Formation of Bonds to
Group-I, -II, and -IIIb Elements, Vol. 13, John Wiley & Sons, ISBN 089573-263-7
Reimer, Ludwig (1993). Image Formation in Low-voltage Scanning Electron
Microscopy. SPIE Press. ISBN 978-0-8194-1206-5.
Cotton, S. A. (1997). "Aspects of the lanthanide-carbon s-bond". Coord. Chem. Rev.
160: 93�127. doi:10.1016/S0010-8545(96)01340-9.
MacDonald, R. P. (1964). "Uses for a Holmium Oxide Filter in Spectrophotometry"
(PDF). Clinical Chemistry. 10 (12): 1117�20. PMID 14240747.
"Holmium Glass Filter for Spectrophotometer Calibration". Archived from the
original on 2010-03-14. Retrieved 2009-06-06.
Levine, Albert K.; Palilla, Frank C. (1964). "A new, highly efficient red-emitting
cathodoluminescent phosphor (YVO4:Eu) for color television". Applied Physics
Letters. 5 (6): 118. Bibcode:1964ApPhL...5..118L. doi:10.1063/1.1723611.
Werts, M. H. V. (2005). "Making Sense of Lanthanide Luminescence". Science
Progress. 88 (2): 101�131. doi:10.3184/003685005783238435.
There exist other naturally occurred radioactive isotopes of lanthanides with long
half-lives (144Nd, 150Nd, 148Sm, 151Eu, 152Gd) but they are not used as
chronometers.
McGill, Ian (2005) "Rare Earth Elements" in Ullmann's Encyclopedia of Industrial
Chemistry, Wiley-VCH, Weinheim. doi:10.1002/14356007.a22_607.
Haxel G, Hedrick J, Orris J (2006). Rare earth elements critical resources for
high technology (PDF). Reston (VA): United States Geological Survey. USGS Fact
Sheet: 087-02. Retrieved 2008-04-19.
Livergood R. (2010). "Rare Earth Elements: A Wrench in the Supply Chain" (PDF).
Center for Strategic and International Studies. Retrieved 2010-10-22.
Chu, Steven. Critical Materials Strategy[permanent dead link] p. 17 United States
Department of Energy, December 2011. Accessed: 23 December 2011.
Bunzil, Jean-Claude; Piguet, Claude (September 2005). "Taking advantage of
luminescent lanthanide ions" (PDF). Chemical Society Reviews. 34 (12): 1048�77.
doi:10.1039/b406082m. PMID 16284671. Archived from the original (PDF) on 18 January
2013. Retrieved 22 December 2012.
Palizban, A. A.; Sadeghi-aliabadi, H.; Abdollahpour, F. (2010-01-01). "Effect of
cerium lanthanide on Hela and MCF-7 cancer cell growth in the presence of
transferring". Research in Pharmaceutical Sciences. 5 (2): 119�125. PMC 3093623.
PMID 21589800.
Yu, Lingfang; Xiong, Jieqi; Guo, Ling; Miao, Lifang; Liu, Sisun; Guo, Fei (2015).
"The effects of lanthanum chloride on proliferation and apoptosis of cervical
cancer cells: involvement of let-7a and miR-34a microRNAs". BioMetals. 28 (5):
879�890. doi:10.1007/s10534-015-9872-6. PMID 26209160.
Pol, A., et al (2014). "Rare Earth Metals Are Essential for Methanotrophic Life in
Volcanic Mudpots". Environ Microbiol. 16 (1): 255�264. doi:10.1111/1462-2920.12249.
PMID 24034209.
Cited sources
Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils (2007). Lehrbuch der Anorganischen
Chemie (in German) (102 ed.). Walter de Gruyter. ISBN 978-3-11-017770-1.
External links
lanthanide Sparkle Model, used in the computational chemistry of lanthanide
complexes
USGS Rare Earths Statistics and Information
Ana de Bettencourt-Dias: Chemistry of the lanthanides and lanthanide-containing
materials
Eric Scerri, 2007, The periodic table: Its story and its significance, Oxford
University Press, New York, ISBN 9780195305739
vte
Periodic table (Large cells)
1 2 3 4 5 6 7 8 9 10 11 12 13
14 15 16 17 18
1
H
He
2
Li
Be
B
C
N
O
F
Ne
3
Na
Mg
Al
Si
P
S
Cl
Ar
4
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Br
Kr
5
Rb
Sr
Y
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Te
I
Xe
6
Cs
Ba
La
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
Ir
Pt
Au
Hg
Tl
Pb
Bi
Po
At
Rn
7
Fr
Ra
Ac
Th
Pa
U
Np
Pu
Am
Cm
Bk
Cf
Es
Fm
Md
No
Lr
Rf
Db
Sg
Bh
Hs
Mt
Ds
Rg
Cn
Nh
Fl
Mc
Lv
Ts
Og
Alkali metal Alkaline earth metal Lan�thanide Actinide Transition metal
Post-?transition metal Metalloid Reactive nonmetal Noble gas Unknown
chemical
properties
vte
Periodic table
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