Chapter III.

Chemistry of the block elements

III.A. General Information on Transition Elements

III.A.1. Definitions

Restrictive definition: a transition element is an element that has a sub-shell.

incomplete;
Extended definition: a transition element is an element that has a sub-shell.
incomplete, in one of its usual oxidation states.

III.A.2. Electronic configuration of the elements

[Ar] Sc You V Cr Mn Fe Co Ni Cu Zn
3d 1 2 3 5 5 6 7 8 10 10
4s 2 2 2 1 2 2 2 2 1 2
[Kr] Y Zr Nb Mo Tc* Ru Rh Pd Ag Cd
4d 1 2 4 5 5 7 8 10 10 10
5s 2 2 1 1 2 1 1 0 1 2
[Xe] The Hf Ta W Re Os Ir Pt Au Hg
4f 0 14 14 14 14 14 14 14 14 14
5d 1 2 3 4 5 6 7 9 10 10
6s 2 2 2 2 2 2 2 1 1 2

III.A.3. General characteristics of the elements

They are metals;

They can exhibit many oxidation states, some of which are negative;
They form numerous complexes;
These complexes are often colorful and paramagnetic;
The electronic configuration of a transition element complex of the form d, withnn = G - x, where
G is the group number and x is the (algebraic) oxidation number of the metal.

III.B. Classification of ligands

III.B.1. Lewis Bases

In the case of complexes of metal cations with intermediate or high oxidation states
(Werner complexes, see III.C.), the metal-ligand bond (or coordination bond) is ensured
by one (or more) pairs of electrons brought by the ligand (dative bond): the ligand is
Lewis base; the metal cation is a Lewis acid.

III.B.1.a. Monodentate ligands

Classification according to the donor element:

halogen: F-, Cl-, Br-, I-.
Examples: [FeF6]3–[FeCl4]–, [HgI4]2–…
• oxygène : H2Oh, oh-, RO-, O2–, O2, O2–, O22–, NO2–...
Examples: [FeII(H2O)6]2+, [CrVIO4]2–, [CoIII(ONO)(NH3)5]2+
• soufre : S2-, R2S, RS-, SCN-....

LC 205 - Inorganic Chemistry - Ch. III 95

 Examples : [MoVIS4]2–, [CoIII(CN)5(SCN)]3–
nitrogen : NH3, NH2-, NH2-, N3-, pyridine, NCS-, N2NO, NO2... -
Examples: [CoIII(NH3)6]3+[OsVINCl5]2–, [RuII(N2)(NH3)5]2+, [CoIII(NCS)(NH3)5]2+,
[FeI(NO)(H2O)5]2+, [IrIII(NO)Cl2(PPh3)2]
carbon: CN–, CH3–...
Examples: [FeIII(CN)6]3-, [W(CH3)6]
-
Note: the SCN ligands- who can bond through sulfur or nitrogen, and NO2, who can be linked
by oxygen or nitrogen are ambidentate. They can also adopt modes of
bridge coordination between two metallic centers (see III.B.1.d.).
Note: the donor atom is underlined.

III.B.1.b. Bidentate ligands

- III
• CH3COCHCOCH3(acetylacetonate: acac). Examples: [Cr (acac) 3],
2- III + III 3–
• C2O4 (oxalate : ox). Examples: [Cr (ox)2(H2O)2] , [Cr (ox)3]
• H2NCH2CH2NH2(ethylenediamine: en). Examples: [CoIIICl2(en)2]+, [CoIII(en)3]3+...
• bipyridine (bpy). Example: [Ru(bpy)3]2+
-
• H2NCH2CO2(glycinate : gly). Example: [Co(gly)3]
Note: the glycinate ion binds through the nitrogen atom and through an oxygen atom of the function.
carboxylate.

III.B.1.c. Multidentate ligands

• NH(CH2CH2NH2)2(dien). Example: [Co(dien)2]3+
• H2NCH2CH2NHCH2CH2NHCH2CH2NH2(trien)
Porphyrins (Por).
4-
• (O2CCH2)2NCH2CH2N(CH2CO2)2(ethylenediaminetetraacetate: edta).
Examples: [Cr (edta)(H2O)] , [Co (edta)] , [Fe (edta)(H2O)]–The ligand edta is pentadentate.
III – III – III

in the complex [CrIII(edta)(H2]– (a carboxylate group is dangling) and hexadentate in the

complexes [CoIII(edta)]– (coordination 6) [FeIII(edta)(H2O)]– (coordinence 7).

III.B.1.d. Bridging ligands

(CN)- Co-NC-Fe(CN)
5 5]
6-

N2: [(NH3)5RuIINNRuII(NH3)5]4+
O22–: [(NH3)5CoIII(O2)CoIII(NH3)5]4+
• O2– : [(NH3)5CoIII(O2)CoIII(NH3)5]5+
- 3)4What (µ-NH
NO : 2[(NH III III
2)(µ-ONO)Co (NH3)4]
4+

III.B.2. Lewis Acids

The stabilization of low oxidation state complexes of transition metals requires

ligands that are not only Lewis bases but also Lewis acids in order to
limit the electronic density on the metal. These ligands have accessible vacant orbitals
(sufficiently low energy) and of suitable symmetry. The carbonyl ligand, CO, is its prototype.
Examples: [Cr0(CO)6] [Fe-II(CO)4]2-...
Note: NO+, CO, N2and CN– are isolectronic. Lewis basicity increases in the order:
NO+ < CO < N2< CN– while Lewis acidity decreases in the order: NO+ CO > N2> CN–.

LC 205 – Inorganic Chemistry – Ch. III 96

III.C. Werner Theory - Stereochemistry of Complexes

III.C.1. Werner's Theory

III.C.1.a. Concept of coordination

Experimental data concerning cobalt(III) complexes:

composition color series number of Cl ions– current formulation

immediately
precipitates by Ag+
Cobalt. chloride36NH
orange
3 lutéo 3 Co(NH3)6]3+, 3Cl-
.
Cobalt(II) chloridepurple
35NH3 purple 2 CoCl(NH3)5]2+, 2Cl-
.
CoCl34NH3 vert pray 1 trans-[CoCl]2(NH3)4]+, Cl-
.
Cobalt(II) chlorideviolet
34NH3 violet 1 cis-[CoCl2(NH3)4]+, Cl-
Cobalt. Chloride33NH
blue-green
3 0 CoCl3(NH3)3]
III.C.1.b. Concept of stereochemistry
CoCl2(NH3)4]2+only presents two geometric isomers;
[Co(en)3]3+and [Co(NO2)2(en)2]+ can be doubled into optical inverses.
These complexes have an octahedral geometry.
• [PtCl2(NH3)2presents two geometric isomers.
This complex is square-shaped.

III.C.2. Stereochemistry of coordination complexes

III.C.2.a. Coordinates and common geometries

Coordination Coordination polyhedron Examples

2 linear [CuCl2]-, [Ag(NH3)2]+

4 tetrahedron CrO4]2-, [MnO4]-, [FeCl4]- ]-, [Ni(CO)4]
4 square plan [Ni(CN)4]2-, [PtCl4]2-
5 triangular bipyramid Copper(I) chloride5]3-, [Ni(CN)5]3-
5 square-based pyramid [Ni(CN)]5]3-, [Co(CN)5]3-
6 octahedron [Cr(H2O)6]3+, [Cr(NH3)6]3+Cr(ox)3]3-
III.C.2.b. Stereoisomerism

III.C.2.b.α. Definitions

• Stereoisomers: molecules that have the same atoms, the same bond sequences but
different by their arrangement in space.
• Enantiomers: an enantiomer is a stereoisomer that is not superimposable on its mirror image.
a mirror. Enantiomers are still sometimes referred to as optical antipodes, due to their action
on the polarization plane of a linearly polarized plane wave: one of the isomers rotates
the plan in one direction (+αthe second, in the otherα).
• Diastereomers: these are stereoisomers that are not enantiomers.
Asymmetric: qualifies a molecule devoid of any element of symmetry.
Asymmetric: qualifies a molecule lacking an improper axis S. n
Chirality: an asymmetric or dissymmetric compound is chiral (it cannot be superimposed on its)
An image in a mirror). A molecule is chiral when it has neither a plane of symmetry nor a center.
of inversion. More precisely, a molecule is chiral if it does not possess an axis
LC 205 - Inorganic Chemistry - Ch. III 97
improper axis of order n (an improper axis of order n corresponds to one or more repetitions of the
next sequence: rotation of 2π/n followed by a reflection with respect to a plane perpendicular to
the axis of rotation). The complexes [Co(en)3]3+cis-cis-cis-[Co(CN) 2(NH3)2H2)O2]
+ and

PtClBrI(py)(NO2)(NH3are chiral.

III.C.2.b.βCoordination complexes 4 or 6

Octahedral complexes
Type Isomers Examples
stereo diastereoisomer
[Mabcdef] 30 15 30 [Pt(Br)(Cl)(I)(NO2)NH3)(py)]
Ma2b2c2] 6 5 2 [Co(CN)2(NH3)2(H2O)2]+
[PtCl(NH)(py)] 2+
2 3 2 2
Ma4b2] 3 2 2 [CoCl2(NH 3)4]+
cis, trans
Ma3b3] 3 2 2 IrCl3(PPh3)3]
sea, do

Complex square plans

Type Isomers Examples
stereo diastereomer enantiomer
[Mabcd] 3 3 0 [Pt(NH)(NH OH)(py)(NO)] +
3 2 2

[Ma2b2] 2 2 0 PtCl2(NH3)2]
{"cis":"cis","trans":"trans"}

Note: a, b, c, d, e, f refer to monodentate ligands.

III.D. Nomenclature of coordination complexes

III.D.1. Formulas

In formulas, the rule is that the metal symbol is placed first; the ligands
ionic follow, then the neutral ones, and the formula of the complex is enclosed in brackets.
Ex: [CoCl(NH3)5]2+, [Fe(CN)6]3-

III.D.2. Names of ligands

III.D.2.a. The names of anionic ligands, whether mineral or organic,

end in -o: -ure becomes -uro; -ate becomes -ato.
nitrides→ nitride, acetate→ acetate
Common usage, however, has many exceptions:
chloride→ chloro, cyanide→ cyanide, oxide→ oxo
III.D.2.b. The names of neutral ligands are retained:
Ex : 1,10-phenanthroline, ethylenediamine, pyridine
There are, however, 4 important exceptions:
H2O→ water, NH3→ amine, CO→ carbonyl, NO→ nitrosyle
III.D.2.c. The names of cationic ligands are preserved.

LC 205 - Inorganic Chemistry - Chapter III 98

 III.D.3. Prefixes

III.D.3.a. Multiplicative prefixes

mono, di, tri, tetra, penta, hexa, hepta, octa, nona,...
III.D.3.b. Structural prefixes
They provide structural information and are written in italics before the name of which we
separate them with a hyphen.
["catena","cyclo","octahedron","cis","trans","mer","fac"]

III.D.4. Names of complexes

The names of the ligands appear before those of the metal, and in alphabetical order, without
take into account the load and without taking into account the multiplier prefix indicating the number of
ligands. The oxidation state of the metal is indicated in Roman numerals in parentheses after the name.
The suffix -ate is used when the complex is anionic. The name of the metal remains unchanged.
when the complex is neutral or cationic.

Ex : [CoCl(NH3)5]Cl2 pentamminechlorocobalt(III) chloride

RuCl3(py)3] fac-trichlorotris(pyridine)ruthenium(III)
K4[Fe(CN)6] potassium hexacyanoferrate(III)
[(NH3)5Co-O-O-Co(NH3)5]4+ µperoxobis[pentamminecobalt(III)]

III.E. Crystal Field Theory

III.E.1. Lifting of degeneracy of orbitals

The crystal field theory is a purely electrostatic model that takes into account the
repulsion between the electrons of the metallic center and the electrons of the ligands. Initially, the
ligands are far away from the metal ion; when we bring them closer, the attraction
Electrostatics ensures the stability of the complex. However, the metal orbitals are destabilized.
by the repulsion exerted by the electrons of the ligands. But they are not all to the same
way: while in the free ion (spherical symmetry) the 5 d orbitals are degenerate, it is not the case
so no more the same in a complex.

LC 205 – Inorganic Chemistry – Ch. III 99

 Representation of the orbitals (cf. chapter I, p. 5) and their interaction with arranged ligands
at the vertices of an octahedron whose center is occupied by the metal ion. The ligands are
represented by negative partial charges; the axes Ox, Oy, Oz are chosen according to the
diagonals of the octahedron

III.E.1.a. Octahedral complexes [ML6]

The ligands are placed along the x, y, and z axes. The examination of the orbitals (cf. chapter I, p.
5) reveals that the orbital ofx2-y2 where the lobes point towards the ligands, is more destabilized than
the d orbitalxy, whose lobes point between the ligands. It is easy to see that the 3 d orbitalsxy,
dxzand dyzhave the same relative orientation with respect to the ligands and therefore undergo the
same effect. If one remembers that the d orbitalz2is a linear combination of the d orbitals2 2 and z -x
dz2-y2it becomes clear that the d orbital
z2 is destabilized in the same way as the d orbital .
2 x2 -yLe
The field exerted by the ligands (crystal field) thus lifts the degeneracy of the d orbitals.
a cubic octahedron, the 5 orbitals separate into two groups, the d orbitalsxy, dyzand dxz
(t)2g on one hand, the d orbitalsx squaredz2 minusgy squaredand from the other part. If we represent
o byΔ the difference
of energy between the two groups of orbitals (ligand field parameter) and if one chooses the
center of the orbitals in the complex (this refers to the level of the orbitals in a complex
In the hypothetical case of spherical symmetry, the energies of the t and
2ge orbitals
g are respectively equal to
-0.4Δ oand +0.6Δ .o

III.E.1.b. Tetrahedral complexes [ML4]

In a tetrahedral complex, the d orbitals split into two groups, as

in the octahedral complexes, but the d orbitalsxy, dyzand dxz(t) are this2 time more
destabilized than the d orbitalsx squared minus y squared
z2and d (e). If one represents by
t Δ the difference in energy between
the two groups of orbitals (ligand field parameter) and if one chooses the barycenter of the
orbitals in the complex (this refers to the level of the orbitals in a hypothetical complex
[ML4In spherical symmetry, the energies of the e and t orbitals 2 are respectively equal to -0.6Δ t
and +0.4Δt .

Note: for the same metal, M, the same ligand, L, and the same metal-ligand distance, one
can establish the relationship:tΔ (4/9)Δ .o

LC 205 – Inorganic Chemistry – Ch. III 100

 III.E.1.c. Symmetry lowering: transition from the octahedron to the square-plane

If starting from an octahedral complex [ML],

6 one gradually moves the two
ligands located on the z-axis, the repulsion of the electrons from the ligands exerts less influence on the d orbitals. xz
and yz
on the d orbital and onxy the d orbital that on
z2 the d orbital2 2This xresults
-y in a raising of
additional degeneration. When the ligands are far away to infinity (transition to the square plane,
the d orbitalz2passes below d. xy
These results are illustrated by the following diagrams:
ion in a field
of symmetry D
ion in a field
4h

(stretched octahedron)
ion in a field of symmetry
of symmetry octahedral dx 2 -y2 #2/2
eg
tetrahedral dz2 dx 2 -y2 d z2
"#2/2
t2
dyz +0.6! o
+0.4! t dxzdxy !o
"0.6! t !t "0.4! o
#1/3
e
dyz t dxzdxy
dz 2 dx 2 -y2 dxzdxy 2g "2# 1/3
dyz

III.E.1.d. Spectrochimical series

For a given metal, ligands can be classified by increasing value ofΔ and for a
given ligand we can classify the metals.
Influence of the ligand:
I- < Br- < S2-< SCN- < Cl- < F- Oh- < C O < H O 2-
2 <4NCS- <2 NH3< py ~ en ~ bipy ~ phen
< NO2<- CH <3CN - - < CO

This series is called the spectrochemical series because the parameter ∆ is most often extracted.
UV-visible spectra. Such a series cannot be explained within the framework of a model.
electrostatics. On the other hand, it can be explained using molecular orbital theory (see LC)
304). We will simply note thatΔ is weak for donor ligandsπ (F–, O2–raised
for the accepting ligandsπ (CO, CN). -
Influence of the metal:
oxidation state: M(II) < M(III) < M(IV)
series: 1 < 2 < 3 (ex: Ni < Pd < Pt)

III.E.2. Stabilization energy due to the crystal field

III.E.2.a. Definition

The stabilization energy of a complex [ML] is n the difference between the energy of
real complex and that of a hypothetical complex of the same composition but with symmetry
spherical. It is given by the expression:
ESCC =Σ ni Ei +δP
i
wherei n is the number of electrons in the energy orbital Ei; δ What is the difference between the numbers of
pairs of electrons in the real complex and in the hypothetical complex; P is the energy
of electron pairing.

LC 205 – Inorganic Chemistry – Ch. III 101

 dn Oh Td
n weak field strong field always weak champion
0.10 0 0 0
1 -0.4Δo -0.4∆o -0.267∆o
2 -0.8∆o -0.8∆o -0.534Δo
3 -1,2∆o -1,2∆o -0.356∆o
4 -0.6∆o -1.6Δo+ P -0.178∆o
5 0 -2.0∆o+ 2P 0
6 -0.4∆o -2.4 deltao+ 2P -0.267∆o
7 -0.8∆o -1.8∆o + P -0.534∆o
8 -1.2 deltao -1,2∆o -0.356∆o
9 -0.6∆o -0.6∆o -0.178∆o
Variation of stabilization energy due to the crystal field (ESCC, in units ofΔ ) depending
o on
of the number of d electrons for weak field octahedral and tetrahedral complexes

Δο

Variation of the ESCC for octahedral complexes in weak field - Graphical representation

III.E.3. Optical properties

The color of many coordination complexes finds its origin in transitions.

electronic transitions between energy levels associated with the configuration ofnof the complex (transitionsd-d).
Thus, the UV-visible absorption spectrum of the complex [Ti(H 2O)6]3+in aqueous solution present
a wide band centered at 493 nm (or 20300 cm)-1that is attributed to the transition of the electron
of level t2gat level egThe intensity of the transition (expressed by the value of the coefficient
(absorption) is weak because the transition does not satisfy certain selection rules (see LC 312).
In this case, the transition energy directly provides the value of ∆.ODetermination
From the absorption spectrum is not always immediate when the metallic cation
has several electrons, but it remains possible.
Note: the color of some complexes originates from transitions.
different from d-d transitions, for example ligand charge transfer transitions →metal
Examples: [Fe(NCS)(H2O)5]2+, [MnO4]–) or internal transitions within the ligands when this
they are themselves colored (cf. LC 312).

LC 205 - Inorganic Chemistry - Ch. III 102

 III.E.4. Magnetic properties

• Octahedral complexes: two electronic distributions are possible for the configurations
d4, d5 , d6 and7 d .
Δo< P high-spin complexes (weak field)
ΔoP spin complexes (strong field)
• Tetrahedral complexes: two electronic distributions are generally possible for the
configurations d 3, d 4, d 5and d6, but the conditionΔ P tis never verified so that all the
Known tetrahedral complexes are high-spin.

III.E.5. Enthalpies of hydration

The enthalpy of hydration corresponds to the reaction:

M2+(g) + H2O(l)→ [M(H2O)6]z+(aq)

M2+ Ca2+ You2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ With2+ Zn2+
Z 20 22 23 24 25 26 27 28 29 30
N (number of electrons d) 0 2 3 4 5 6 7 8 9 10
-ΔH, kJ mol-1 2466 2732 2778 2795 2736 2845 2916 2996 3000 2933

2+ Mn and
If we limit ourselves to the ions Ca, 2+ Zn, we
2+ observe that the enthalpy of hydration
increases (in absolute value) regularly by Ca in Zn,2+in accordance
2 with the increase of the
effective nuclear charge. For other ions, it is (in absolute value) higher than one would expect.
it waits for it. If one corrects the effects of the crystal field by subtracting the contribution of the ESCC, one
obtains a fairly regular curve.

Variation of the hydration enthalpy (kJ mol) of-1cations M from 2+the 1st transition series
(dashed line: corrected values of the ESCC); according to K.F. Purcell and J.C. Kotz, Inorganic
Chemistry, Saunders, 1977, p. 554.

LC 205 – Inorganic Chemistry – Ch. III 103

 III.E.6. Stability of complexes

III.E.6.a. Definitions

Mz+ + nL→ [ML z+

n ]

[MLnz+]
! n= = K1 K2 ... Kn
[Mz+][L]n

ΔG0 = ΔH0 - TΔS0 = -RTLnβn

The two factors, enthalpic and entropic, must be taken into account. The chelate effect.
is primarily an entropic effect: chelation leads to an increase in the number of particles
independent in solution, whereas substitution reactions with monodentate ligands do not
is accompanied by no change in the number of particles. The practical importance of this effect
is considerable: the majority of reagents used in complexometric analysis are ligands
multidentates (e.g. EDTA); in biomolecules, most cation binding sites
métalliques sont des ligands chélatants ou macrocycliques.

III.E.6.b. General trends

The behavior of metal cations from the s block (groups 1 and 2) and cations of
electron-poor transitions can be rationalized using a simple electrostatic model: the
the formed complexes are all the more stable as the oxidation state of the metal is higher and that the
the cation radius is smaller.
Li+ Na+ K+ • Mg2+Ca2+Sr2+ • Al3+> Sc3+Y3+
• You > Sc Ca >
4+ 3+ 2+ +
Apparent exceptions can be explained by the role of the ESCC and that of the
covalence whose importance increases as the number of electrons increases.
In the absence of any lifting of degeneracy of the d orbitals, the formation constants of the
complexes formed by the M ions z+ belonging to the same transition series should increase
regularly depending on Z since the effective nuclear charge Z increaseseffand the radius
the ion decreases. Experimentally, the same irregularities are observed as for the enthalpies
of hydration and the interpretation is the same: after correcting for the effects of the ligand field, one
It is noted that logK
n increases regularly as a function of Z.
The trend is illustrated on the following page by the evolution of the formation constants of
complexes [M(en)(H2O)]2+.

LC 205 – Chimie Inorganique – Ch. III 104

 Variation of standard enthalpy of formation for complexes of cations M with 2+
ethylenediamine. Comparison of experimental values and those predicted by field theory
crystalline.

Note: Cu(II) complexes show an anomaly; indeed, the complexes with 1 and 2
ligands (en) are more stable, while the complex (en)3is less stable than anticipated
the extrapolation between Ni(II) and Zn(II). These anomalies can be explained by the distortion of the octahedron of
coordination (Jahn-Teller effect). The Jahn-Teller effect mainly affects complexes
4
octahedral configurations of d (high-spin) or d (cf.9 LC 304).

III.E.7. Reactivity of coordination complexes

It is essential to distinguish between the kinetic aspects and the aspects

thermodynamics. According to the value of its formation constant (thermodynamic), a complex
is stable or unstable. According to the rate constant of its substitution reactions, a complex is
labile (quick reactions) or inert (slow reactions, requiring at least one minute, sometimes
much more).
We will here limit ourselves to considering the case of dissociative type reactions (two others
mechanisms, namely interchange type and associative type, have been identified, see LC 312)
This is the case for the majority of the substitution reactions of octahedral complexes.
cobalt(III). Depending on whether the intermediate of the pyramid with a square base formed by detachment of the
The departing group rearranges itself or not into a trigonal bipyramid, there is retention or not of the
configuration.

The differences in reactivity depending on the metal can be explained using field theory.
crystalline: the initial complex (i) and the intermediate (int) are both stabilized by the field
crystalline. When the intermediate is less stabilized than the initial state, the complex is poorly
reactive. The difference ESCC(int) - ESCC(i) is called activation energy due to the crystal field
(EACC).
LC 205 - Inorganic Chemistry - Ch. III 105
Calculation of the EACC in the case where the intermediate is a square-based pyramid (it is assumed that the
The initial complex and the intermediate complexes have the same spin state.

n ESCC(i) in unitΔ o ESCC(int) in unitΔ o EACC in unitΔ o

high spin bas-spin top spin bas-spin top spin bas-spin
0, 5, 10 0 0 0 0 0 0
1, 6 0.400 0.457 0.057
2, 7 0.800 - 0.914 0.114
3, 8 1,200 1,000 + 0.200
4, 9 0.600 0.914 0.314
4 1,600 1,457 + 0.143
5 2,000 1,914 + 0.086
6 2,400 2,000 + 0.400
7 1,800 - 1,914 0.114

It is explained that reactivity decreases in the order:

d5(bas-spin) > d4(bas-spin) > d8, d3> d6(bas-spin)
The complexes of chromium(III), cobalt(III), and platinum(IV) are particularly inert.

LC 205 - Inorganic Chemistry - Ch. III 106