Química

Inorgánica II
Dr. Hiram Isaac Beltrán Conde
 Parte 4

Tipos de enlace y reactividad

en compuestos de coordinación
The history of modern coordination
chemistry has been the subject of
several books, of which perhaps the
best known are those by George B.
Kauffman. By necessity they all
highlight Alfred Werner, "the Father
of Coordination Chemistry" who in
1893, proposed the octahedral
configuration of transition metal
complexes and in 1913 received the
first Nobel prize in Inorganic
Chemistry.
 Structures of Coordination Complexes: The ammonia complexes of
Co(III) = Co3+

How did Werner deduce the structure of coordination complexes?

Composition Ions released Color

CoCl3.6NH3 3 “free” Cl- ions Orange-Yellow

CoCl3.5NH3 2 “free” Cl- ions Purple

CoCl3.4NH3 1 “free” Cl- ions Green

CoCl3.3NH3 0 “free” Cl- ions Green

In all of these complexes there are no free NH3 molecules

(No reaction with acid)
 “free” Cl- is not in sphere; all NH3 molecules are (is) in sphere

Compound 1: CoCl3.6NH3 = [Co(NH3)6]3+(Cl-)3 = [Co(NH3)6](Cl)3

Conclude: 3 free Cl- ions, complex = [Co(NH3)6]3+

Compound 2: CoCl3.5NH3 = [Co(NH3)5Cl]2+(Cl-)2 = [Co(NH3)5Cl](Cl)2

Conclude: 2 free Cl- ions, complex = [Co(NH3)5Cl]2+

Compound 3: CoCl3.4NH3 = [Co(NH3)4Cl2]1+(Cl-) = [Co(NH3)4Cl2](Cl)

Conclude: 1 free Cl- ion, complex = [Co(NH3)4Cl2]1+

Compound 4: CoCl3.3NH3 = [Co(NH3)3Cl3] = complex

No free Cl- ions, both Cl- and NH3 in sphere

Coordination complexes: Three dimensional structures

NH3 Cl
. H3N Co NH3 .
CoCl3 5NH3 H3N Co NH3
CoCl3 6NH3
H3N NH3 H3N NH3
NH3 NH3
Cl- Cl- Cl- Cl- Cl-

Cl Cl
H3N Co Cl H3N Co NH3
.4NH
CoCl3
Isomers!
3 H3N NH3 H3N NH3
NH3 Cl
Cl- Cl-
Some definitions:
A coordination compound, sometimes called a coordination
complex, contains a central metal atom or ion surrounded by a
number of oppositely charged ions or neutral molecules
(possessing lone pairs of electrons) which are known as ligands.

If a ligand is capable of forming more than one bond with the

central metal atom or ion, then ring structures are produced
which are known as Metal Chelates, the ring forming groups are
described as chelating agents or polydentate ligands.

The coordination number of the central metal atom or ion is the

total number of sites occupied by ligands. Note: a bidentate
ligand uses two sites, a tridentate three sites etc.
Coordination Complexes
n When bases (“ligands”) interact with metal
ions, a coordination complex results. This ferrocene
interaction is created by a neutral or anionic
molecule (ligand) donating at least one
electron pair to the Lewis acidic metal ion

n The bonding in these complexes results from

donation of an electron pair by the ligand to
the metal ion (coordinate covalent bond)

n Metal ions commonly coordinate four, six, or

more ligands.

n These types of complexes bridge inorganic

chemistry, organometallic chemistry (M-C
bonds) and biochemistry (porphyrins,
proteins, etc.)
N N N
Coordination Complexes
Ligands:
Ligands:
Ligands:
 Ligands:
molecular Lewis Lewis donor coordination
formula base/ligand acid atom number

[Zn(CN)4]2- CN- Zn2+ C 4

[PtCl6]2- Cl- Pt4+ Cl 6

[Ni(NH3)6]2+ NH3 Ni2+ N 6

Mono-dentate
Monodentate Ligands

(this one is actually bidentate)

ambidentate
Polydentate Ligands
 Coordinative Bond:

A covalent bond is formed by two atoms sharing a pair of

electrons. The atoms are held together because the electron pair
is attracted by both of the nuclei.

In the formation of a simple covalent bond, each atom supplies

one electron to the bond - but that doesn't have to be the case.
A co-ordinate bond (also called a dative covalent bond) is a
covalent bond (a shared pair of electrons) in which both
electrons come from the same atom.
 Coordinative Bond:
The reaction between ammonia and hydrogen chloride

If these colourless gases are allowed to mix, a thick white smoke

of solid ammonium chloride is formed.
Ammonium ions, NH4+, are formed by the transfer of a
hydrogen ion from the hydrogen chloride to the lone pair of
electrons on the ammonia molecule.
 Coordinative Bond:
The reaction between ammonia and
hydrogen chloride

When the ammonium ion, NH4+, is formed, the

fourth hydrogen is attached by a dative covalent
bond, because only the hydrogen's nucleus is
transferred from the chlorine to the nitrogen.
The hydrogen's electron is left behind on the
chlorine to form a negative chloride ion.

Once the ammonium ion has been formed it is

impossible to tell any difference between the
dative covalent and the ordinary covalent bonds.
Although the electrons are shown differently in
the diagram, there is no difference between them
in reality.
 Coordinative Bond:
Representing co-ordinate bonds

In simple diagrams, a co-ordinate bond is shown by an arrow. The arrow

points from the atom donating the lone pair to the atom accepting it.
 Coordinative Bond:
Dissolving hydrogen chloride in water to make hydrochloric acid

Something similar happens. A hydrogen ion (H+) is transferred from the

chlorine to one of the lone pairs on the oxygen atom.

The H3O+ ion is variously called the hydroxonium ion, the hydronium
ion or the oxonium ion.
 Coordinative Bond:

In an introductory chemistry course, whenever you have talked about

hydrogen ions (for example in acids), you have actually been talking
about the hydronium ion. A raw hydrogen ion is simply a proton, and
is far too reactive to exist on its own in a test tube.

If you write the hydrogen ion as H+(aq), the "(aq)" represents the
water molecule that the hydrogen ion is attached to. When it reacts
with something (an alkali, for example), the hydrogen ion simply
becomes detached from the water molecule again.

Note that once the co-ordinate bond has been set up, all the
hydrogens attached to the oxygen are exactly equivalent. When a
hydrogen ion breaks away again, it could be any of the three.
 Coordinative Bond:
The reaction between ammonia and boron trifluoride, BF3

If you have recently read the page on covalent bonding, you may remember
boron trifluoride as a compound which doesn't have a noble gas structure
around the boron atom. The boron only has 3 pairs of electrons in its bonding
level, whereas there would be room for 4 pairs. BF3 is described as being
electron deficient.
The lone pair on the nitrogen of an ammonia molecule can be used to
overcome that deficiency, and a compound is formed involving a co-ordinate
bond.
 Coordinative Bond:
The reaction between ammonia and boron trifluoride, BF3

Using lines to represent the bonds, this could be drawn more simply as:

The second diagram shows another way that you might find co-ordinate
bonds drawn. The nitrogen end of the bond has become positive because
the electron pair has moved away from the nitrogen towards the boron -
which has therefore become negative. We shan't use this method again -
it's more confusing than just using an arrow.
 Coordinative Bond:
The structure of aluminium chloride

Aluminium chloride sublimes (turns straight from a solid

to a gas) at about 180°C. If it simply contained ions it
would have a very high melting and boiling point because
of the strong attractions between the positive and
negative ions. The implication is that it when it sublimes
at this relatively low temperature, it must be covalent.
The dots-and-crosses diagram shows only the outer
electrons.

AlCl3, like BF3, is electron deficient. There is likely to be

a similarity, because aluminium and boron are in the
same group of the Periodic Table, as are fluorine and
chlorine.
Adduct effect
The LUMO and
HOMO are called
frontier orbitals. If
there is a net lowering
of energy, the adduct
is stable.
 BF3 + NH3
The LUMO of the acid, the HOMO of the
base and the adduct are shown below:
 The Nature of the Adduct
Hard acid/hard base adducts tend to have
more ionic character in their bonding. These are
generally more favored energetically.

Soft acid/soft base adducts are more

covalent in nature.
Ligands and oxidation states:
Chelating Ligands
 Chelating Ligands
n Some molecules/ions are capable of donating electron pairs
through more than one atom at once. This interaction results
in the formation of a chelate (pronounced: key-late) ring
n Chelating ligands tend to form very stable complexes with
metal ions. Some ligands are even capable of forming more
than one chelate ring (example EDTA: ethylene diamine
tetraacetic acid)
Nice to know: five- and six
membered rings tend to be the
most stable, and more chelate
rings means more stable

How many chelate rings in this structure?

From Harris, Quantitative Chemical Analysis, 6th Ed.

The Chelate Effect

n Polydentate ligands form more stable complexes with transition

metal ions than monodentate ligands. They can easily replace
monodentate ligands in displacement reactions
n For example, ethylene diamine (en) will replace ammonia in
[Cd(NH3)4]2+
[Cd(NH3)4]2+(aq) + 2en(aq) D [Cd(en)2]2+(aq) + 4NH3(aq)
n The additional stability of a chelate complex over a monodentate
one is known as the chelate effect, and is thermodynamic in origin

H2N :
H2N
a bidentate ligand
NH2
en = : NH2 M z+ denticity = # of donor
atoms in a ligand
The Chelate Effect

Chelating ligands bonded to metal – rings – chelate rings

any number of atoms in the ring
most common – five or six atoms, including metal

"The adjective chelate, derived from the great claw or

chela (chely - Greek) of the lobster, is suggested for the
groups which function as two units and fasten to the
central atom so as to produce heterocyclic rings."
The Chelate Effect

n The chelate effect is a result of an entropy increase, and is not so much an

enthalpic effect:
DG = DH - TDS
Cd2+(aq) + 4NH3(aq) D [Cd(NH3)4]2+(aq)
DHo = -52.5kJ/mol; DSo = -41.9 J/K.mol

Cd2+(aq) + 2en(aq) D [Cd(en)2]2+(aq)

DHo = -55.7 kJ/mol; DSo = +10.4 J/K.mol
n It is seen in the reaction below that four monodentate ligands are displaced by
two bidentate ligands, resulting in a greater degree of disorder (DSo = +52.3
J/K.mol):

[Cd(NH3)4]2+(aq) + 2en(aq) D [Cd(en)2]2+(aq) + 4NH3(aq)

Mainly an entropy effect.

Cu(H2O)4(NH3)2]2+ + en = [Cu(H2O)4(en)]2+ + 2 NH3

When ammonia molecule dissociates = swept off in solution and

the probability of returning is remote

When one amine group of en dissociates from complex

ligand retained by end still attached so the nitrogen atom cannot
move away – swings back and attach to metal again. Therefore
the complex has a smaller probability of dissociating

Enthalpy effect (not as important)

Nomenclature
Nomenclature
Nomenclature

Name the following

 Nomenclature

Draw structures for the following

 Isomers:
Primarily in coordination numbers 4 and 6
Arrangement of ligands in space, but also the ligands themselves

Ionization isomers:
Isomers can produce different ions in solution e.g.
[PtCl2(NH3)4]Br2 [PtBr2(NH3)4]Cl2
Polymerization isomers:
Loose term, “same stoichiometry, different
arrangement in space

Seven compounds with formula Co(NH3)3(NO2)3

Coordination isomers:

[Co(NH3)6]3+ [Cr(NH3)6]+3 [Co(CN)6]-3 [Cr(CN)6]-3

Linkage isomers:

e.g. Nitro and nitrito, N

or O coordination
possible
Geometrical Isomerism

n Two species having the same molecular formula

and the same structural framework, but having
different spatial arrangements of atoms around a
central atom or double bond
n Exists in
n Square planar species: Pt(PPh3)2Cl2
n Octahedral species: SnMe2F4, SH3F3
n Trigonal bipyramidal species: Fe(CO)4PPh3
n Double bonds (cis-, trans-): 2-butene
cis-, trans- Isomerism
For square planar systems

Cl NH3 Cl NH3
Pt Pt
Cl NH3 NH3 Cl

cis-Pt(NH3)2Cl 2 trans-Pt(NH3)2Cl 2
For hexacoordinate systems other species can also occur
mer- and fac- Isomerism

X X
Y Y
Y M X X M X
X Y
Y Y

fac-MX 3Y 3 mer-MX 3Y 3
For M(X)3(Y)3 systems there is
facial and meridian
For M(X)3(Y)(Z) systems there is also facial and
meridian but Y or Z must be a bidentate ligand

Are “stereo” isomers also

Possible? An analogy to organic
Chirality. Molecules which can
Rotate light.
 Optical Isomerism

n Similar to carbon compounds, tetrahedral complexes

will also exhibit optical isomerism (chiral complexes).
Octahedral complexes incorporating at least two
bidentate ligands are also chiral.
“propeller complexes”

N N
N N N N
M M
N N N N
N N

(no relation)
L D
 Optical Isomerism

n cis-complexes of this type exhibit this type of isomerism,

but not trans-
mirror plane

N1 N1
N2 Cl Cl N2
Co Co
N3 Cl Cl N3
N4 N4

rotate 180
o

N1
N3 Cl
Co
N2 Cl
N4
Enantiomers (non-superimposable mirror images)
Two coordination complexes which are enantiomers

NH3 NH3
H3N Co Cl Cl Co NH3
H2O Cl Cl H2O
H2O H2O
 Chirality: the absence of a plane of symmetry
Enantiomers are possible

A molecule possessing a plane of symmetry is achiral and a superimposible on

its mirror image
Enantiomers are NOT possible

Are the following chiral or achiral structures?

Plane of symmetry No plane of symmetry

Achiral (one structure) Chiral (two enantiomer)
Which are enantiomers (non-superimposable mirror images) and which are
identical (superimposable mirror images)?
 Polydentate Ligands
n Other interesting polydentate ligands come from
the crown ether class of compounds
What types of isomers can exist for
the following complexes?

n [Ru(NH3)3(OH2)3]2+
bpy
n Fe(CO)4Cl2
n Ru(bpy)3 N N

n Ru(bpy)2Cl2
n Ni(CO)2Br2 N
N N
n Cu(NH3)(OH2)BrCl tpy

n [Ru(tpy)2]2+