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COORDINATION COMPOUNDS

INTRODUCTION :- A coordination
complex is the product of a Lewis acid-base reaction in which
neutral molecules or anions (called ligands) bond to a central
metal atom (or ion) by coordinate covalent bonds.
• Ligands are Lewis bases - they contain at least one pair of
electrons to donate to a metal atom/ion. Ligands are also
called complexing agents.
• Metal atoms/ions are Lewis acids - they can accept pairs of
electrons from Lewis bases.
• Within a ligand, the atom that is directly bonded to the metal
atom/ion is called the donor atom.
• A coordinate covalent bond is a covalent bond in which one
atom (i.e., the donor atom) supplies both electrons. This
type of bonding is different from a normal covalent bond in
which each atom supplies one electron.
• If the coordination complex carries a net charge, the
complex is called a complex ion.
• Compounds that contain a coordination complex are
called coordination compounds.
• Coordination compounds and complexes are distinct
chemical species - their properties and behavior are
different from the metal atom/ion and ligands from which
they are composed.
• The coordination sphere of a coordination compound or
complex consists of the central metal atom/ion plus its
attached ligands. The coordination sphere is usually
enclosed in brackets when written in a formula.
• The coordination number is the number of donor atoms
bonded to the central metal atom/ion.
1. [Co(NH3)6]Cl3 hexaamminecobalt (III) chloride 6 +3
2. K[AuCl4] Potassium tetrachloroaurate(III) 4 +3
3. Cu2[Fe(CN)6] copper(II) hexacyanoferrate(II) 6 +2
4. [Pt(NH3)6]Cl4 hexaammineplatinum(IV) chloride 6 +4
5. [Cu(NH3)4(H2O)2]Cl2 tetraamminediaquacopper(II) chloride 6 +2
6. Cr(CO)6 hexacarbonylchromium (0) 6 0
7. K3[CoF6] potassium hexafluorocobaltate(III) 6 +3
bis(ethylenediamine)platinum(II)
8. [Pt(en)2]CO3 4 +2
carbonate

9. [Ni(H2O)6]Cl2 hexaaquanickel(II) chloride 6 +2


10 [Zn(en)F2] (ethylenediamine)difluorozinc 4 +2
11. [Cr(NH3)5(NO2)]2+ pentaamminenitritochromium(III) ion 6 +3
12. Ba[FeBr4]2 barium tetrabromoferrate(III) 4 +3
dibromobis(ethylenediamine)cobalt(III)
13. [Co(en)2Br2]2SO4 6 +3
sulfate
14. [Ag(NH3)2]Cl diamminesilver chloride 2 +1
15. [Cu(CN)4]3- tetracyanocuprate(I) ion 4 +1

➢ Why are coordination compounds


Formed?
Originally, a complex implied a reversible association of
molecules, atoms, or ions through such weak chemical bonds.
As applied to coordination chemistry, this meaning has
evolved. Some metal complexes are formed virtually
irreversibly and many are bound together by bonds that are
quite strong.
❖The transition elements and main group elements can form
coordination compounds, or complexes in which a central
metal atom or ion is bonded to one or more ligands by
coordinate covalent bonds. Ligands with more than one
donor atom are called polydentate ligands and form
chelates.
Color of Transition Metal Complexes
The variety of color among transition metal complexes has
long fascinated the chemists. For example, aqueous solutions
of [Fe(H2O)6]3+ are red, [Co(H2O)6]2+ are pink,
[Ni(H2O)6]2+ are green, [Cu(H2O)6]2+ are blue and [Zn(H2O)6]2+
are colorless. Although the octahedral [Co(H2O)6]2+ are pink,
those of tetrahedral [CoCl4]2- are blue. The green color of
[Ni(H2O)6]2+ turns blue when ammonia is added to give
[Ni(NH3)6]2+. Many of these facts can be rationalized from CFT.

Why we see Color?


When a sample absorbs light, what we see is the sum of the
remaining colors that strikes our eyes. If a sample absorbs all
wavelength of visible light, none reaches our eyes from that
sample, and then the sample appears black. If the sample
absorbs no visible light, it is white or colorless. When the
sample absorbs a photon of visible light, it is its
complementary color we actually see. For example, if the
sample absorbed orange color, it would appear blue; blue and
orange are said to be complementary colors.

Color of Coordination Complexes


The color of coordination complexes arises from electronic
transitions between levels whose spacing corresponds to the
wavelengths available in the visible light. In complexes, these
transitions are frequently referred to as d-d transitions
because they involve the orbitals that are mainly d in character
(for examples: t2g and eg for the octahedral complexes and e
and t2 for the tetrahedral complexes). Obviously, the colors
exhibited are intimately related to the magnitude of the
spacing between these levels.
Since this spacing depends on factors such as the geometry
of the complex, the nature of the ligands, and the oxidation
state of the central metal atom, variation on colors can often
be explained by looking carefully at the complexes
concerned. Below are a few examples to illustrate this
▪ The variation in the color of the Cr(III) complexes can be
explained following similar arguments

[V(H2O)6]3+ [V(H2O)6]2+
V(III) = d2 ion V(II) = d3 ion violet light
absorbed yellow light absorbed
complex appears yellow complex appears violet
importance of coordination compounds

Application
Coordination compounds are used as catalysts for many
industrial processes and have many applications in
qualitative/quantitative chemical analysis within analytical
chemistry. The of coordination compounds has
importance in biological system, the coordination
compounds play a vital role in metallurgy and medicine.
Coordination compounds are used as catalysts for many
industrial processes and have many applications in
qualitative/quantitative chemical analysis within analytical
chemistry. The of coordination compounds has importance in
biological system, the coordination compounds play a vital role
in metallurgy and medicine. for example it issued to detect
cupric ions in the salt, when copper sulphate solution is mixed
with aqueous ammonia, a deep blue complex soluble in water
is formed.
There is a application of complexes in metallurgy as
follows:

(a) Noble metals like silver and gold are extracted from their
ore by the formation of cyanide complexes - dicyanoargentite
and dicyanoaurate

(b) Metals can be purified by the formation and subsequent


decomposition of their coordination compounds.
Nickel can be purified by its reaction with carbon monoxide to
form the volatile complex, tetracarbonyl Nickel (0), which is
decomposed thermally to yield pure Nickel.

The application of complexes in biological systems as


follows:
(a) The hemoglobin red pigment of blood that acts as oxygen
carrier is a coordination compound of iron.
(b) There is so many enzymes that regulate biological
processes are metal complexes.
Carboxypeptidase is a protease enzyme that hydrolytic
enzyme important in digestion, contains a zinc ion coordinated
to several amino acid residues of the protein.

The applications of coordination compounds as catalysts


in industrial processes as follows:
(a) In the polymerization of ethene, The Ziegler-Natta catalyst
is used which is a combination of titanium tetrachloride and tri
ethyl aluminum.
(b) In the hydrogenation of alkenes, a complex metal catalyst
is used

The applications of coordination compounds in analytical


chemistry as follows:
(a) In the qualitative methods of analysis, complex formation is
of immense importance in the identification and separation of
most inorganic ions.
(When copper sulphate solution is mixed with aqueous
ammonia, a deep blue complex soluble in water is formed.
This reaction is used to detect cupric ions in the salt).
(b) The water hardness is estimated by titration with the
sodium salt of EDTA, the calcium and magnesium ions in hard
water forms the stable complexes, magnesium EDTA and
calcium EDTA.
Examples of ambidentate ligands

SCN- is an example of an ambidentate ligand. This is because


it can bond to a coordination center through nitrogen as well
as sulphur. The below image shows how SCN- can act as an
ambidentate ligand.

As you can see, SCN- can bond either through the sulphur
atom or the nitrogen atom, but not at the same time.
Another example of an ambidentate ligand is NO2-. This ion
can bind to a central atom through either the nitrogen or one
of the oxygen atoms, but again, not at the same time.

NOMENCLATURE OF COORDINATION
COMPOUNDS
IUPAC RULE
INTRODUCTION
According to the Lewis base theory, ligands are Lewis bases
since they can donate electrons to the central metal atom. The
metals, in turn, are Lewis acids since they accept electrons.
Coordination complexes consist of a ligand and a metal
center cation. The overall charge can be positive, negative, or
neutral. Coordination compounds are complex or contain
complex ions, for example:
• Complex Cation: [CO(NH3)6]3+
• Complex Anion: [CoCl4(NH3)2]−
• Neutral Complex: [CoCl3(NH3)3][CoCl3(NH3)3]
• Coordination Compound: K4[Fe(CN)6]

A ligand can be an anion or a neutral molecule that donates


an electron pair to the complex (NH3, H2O, Cl-). The number of
ligands that attach to a metal depends on whether the ligand
is monodentate, bidentate, or polydentate. For more
information, see Ligands and Chelation. To begin naming
coordination complexes, here are some things to keep in
mind.

1. Ligands are named first in alphabetical order.


2. The name of the metal comes next.
3. The oxidation state of the metal follows, noted by a
Roman numeral in parentheses (II, IV)

Rule 1: Anionic Ligands


Ligands that act as anions which end in "-ide" are
replaced with an ending "-o" (e.g., Chloride → Chloro).
Anions ending with "-ite" and "-ate" are replaced with
endings "-ito" and "-ato" respectively (e.g., Nitrite →
Nitrito, Nitrate → Nitrato)
Table 1: Anionic Monodentate Ligands
Molecular Ligand Name Molecular Ligand
Formula Formula Name
F- Fluoro OH- Hydroxo
Cl- Chloro SO42- Sulfato
Br- Bromo S2O32- Thiosulfato
I- Iodo Nitrito-N-;
NO2-
Nitro
O2- Oxo ONO- Nitrito-O-;
Nitrito
CN- Cyano SCN- Thiocyanato-S-;
Thiocyanato
NC- Isocyano NCS- Thiocyanato-N-;
Isothiocyanato
Rule
2: Neutral Ligands
Most neutral molecules that are ligands carry their normal
name. The few exceptions are the first four on the chart:
ammine, aqua, carbonyl, and nitrosyl.

Table 2 : Select Neutral Monodentate Ligands.Note:


Ammine is spelled with two m's when referring to a
ligand. Amines are a class of organic nitrogen-
containing compounds.
Molecular Ligand Name
Formula of
Ligand
NH3 Ammine

H2O Aqua

CO Carbonyl

NO Nitrosyl

CH3NH2 Methylamine

C5H5N Pyridine

Polydentate ligands follow the same rules for anions and


neutral molecules.
Short name Extended name

en
Ethylenediamine

ox2- Oxalato

EDTA4- Ethylenediaminetetraacetato

Table 3: Select Polydentate ligands

RULE 3: LIGAND MULTIPLICITY


The number of ligands present in the complex is indicated with
the prefixes di, tri, etc. The exceptions are polydentates that
have a prefix already in their name (en and EDTA4- are the
most common). When indicating how many of these are
present in a coordination complex, put the ligand's name in
parentheses and use bis, tris, and tetrakis.

Table 4: Prefixes for indicating number of ligands in a complex

Number of Ligands Monodentate Ligands Polydentate


Ligands

1 mono -

2 di bis

3 tri tris
4 tetra tetrakis

5 penta -

6 hexa -
Prefixes always go before the ligand name; they are not taken
into account when putting ligands in alphabetical order. Note
that "mono" often is not used. For example, [FeCl(CO)2(NH3)3]2+
would be called triamminechlorodicarbonyliron(III) ion.
Remember that ligands are always named first, before the
metal is
EXERCISE 1
What is the name of this complex ion: [CrCl2(H2O)4]?
SOLUTION
Let's start by identifying the ligands. The ligands here are Cl and
H2O. Therefore, we will use the monodentate ligand names of
"chloro" and "aqua". Alphabetically, aqua comes before chloro, so
this will be their order in the complex's name. There are 4 aqua's
and 2 chloro's, so we will add the number prefixes before the names.
Since both are monodentate ligands, we will say
"tetra[aqua]di[chloro]".
Now that the ligands are named, we will name the metal itself. The
metal is Cr, which is chromium. Therefore, this coordination complex
is called tetraaquadichlorochromium(III) ion. See the next section for
an explanation of the (III).

EXERCISE 1
What is the name of this.complex ion: [CoCl2(en)2]+?
SOLUTION
There are two chloro and ethylenediamine ligands. The metal is Co,
cobalt. We follow the same steps, except that en is a polydentate
ligand with a prefix in its name (ethylenediamine), so "bis" is used
instead of "bi", and parentheses are added. Therefore, this
coordination complex is called dichlorobis(ethylenediamine)cobalt(III)
ion.
RULE 4: THE METALS
When naming the metal center, you must know the formal metal
name and the oxidation state. To show the oxidation state, we use
Transition Latin
Metal
Iron Ferrate
Copper Cuprate

Tin Stannate

Silver Argentate

Lead Plumbate

Gold Aurate
Roman numerals inside parenthesis. For example, in the problems
above, chromium and cobalt have the oxidation state of +3, so that is
why they have (III) after them. Copper, with an oxidation state of +2,
is denoted as copper(II). If the overall coordination complex is an
anion, the ending "-ate" is attached to the metal center. Some metals
also change to their Latin names in this situation. Copper +2 will
change into cuprate(II). The following change to their Latin names
when part of an anion complex:
Table 5: Latin terms for Select Metal Ion
The rest of the metals simply have -ate added to the end (cobaltate,
nickelate, zincate, osmate, cadmate, platinate, mercurate, etc. Note
that the -ate tends to replace -um or -ium, if present).
Finally, when a complex has an overall charge, "ion" is written after it.
This is not necessary if it is neutral or part of a coordination
compound (Example 3). Here are some examples with determining
oxidation states, naming a metal in an anion complex, and naming
coordination compounds.
Examples Give the systematic names for the following coordination
compounds:
1. [Cr(NH3)3(H2O)3]Cl3
Answer: triamminetriaquachromium(III) chloride
Solution:
• The complex ion is found inside the parentheses. In this
case, the complex ion is a cation.
• The ammine ligands are named first because alphabetically,
“ammine” comes before “aqua.”
• The compound is electrically neutral and thus has an overall
charge of zero. Since there are three chlorides associated
with one complex ion and each chloride has a –1 charge, the
charge on the complex ion must be +3.
• From the charge on the complex ion and the charge on the
ligands, we can calculate the oxidation number of the metal.
In this example, all the ligands are neutral molecules.
Therefore, the oxidation number of chromium must be the
same as the charge of the complex ion, +3.

2. K4[Fe(CN)6]
Answer: potassium hexacyanoferrate(II) Solution:

• Potassium is the cation, and the complex ion is the anion.


• Since there are 4 K+ associated with the complex ion (each
K+ having a +1 charge), the charge on the complex ion must
be - 4.
• Since each ligand carries –1 charge, the oxidation number of
Fe must be +2.
• The common name of this compound is potassium
ferrocyanide.

3. Pt(NH3)2Cl4
Answer: diamminetetrachloroplatinum(IV)
Solution:
• This is a neutral molecule because the charge on Pt+4
equals the negative charges on the four chloro ligands.
• If the compound is [Pt(NH3)2Cl2]Cl2, even though the
number of ions and atoms in the molecule are identical to
the example, it should be named:
diamminedichloroplatinum(IV) chloride because the
platinum in the latter compound is only four coordinated
instead of six coordinated.

4. Fe(CO)5
Answer: pentacarbonyliron(0) Solution:

• Since it is a neutral complex, it is named in the same way


as a complex cation. The common name of this
compound, iron carbonyl, is used more often.
5. [Pt(H2NCH2CH2NH2)2Cl2]Cl2
Answer: dichlorobis(ethylenediamine)platinum(IV) chloride
Solution:
• Since Ethylenediamine is a bidentate ligand, the prefix bis-
is used instead of the prefix di-.

6. [Co(H2NCH2CH2NH2)3]2(SO4)3
Answer: tris(ethylenediamine)cobalt(III) sulfate
Solution:
• The sulfate has a charge of –2 and is the counter anion in
this molecule.
• Since it takes 3 sulfates to bond with two complex cations,
the charge on each complex cation must be +3.
• Since ethylenediamine is a neutral molecule, the oxidation
number of cobalt in the complex ion must be +3.
• Again, remember that you never have to indicate the
number of cations and anions in the name of an ionic
compound.
The Jahn-Teller Theorem
In a nonlinear molecule, if degenerate orbitals are asymmetrically
occupied, a distortion will occur to remove the degeneracy.
(or)
In an electronically degenerate state, a nonlinear molecule
undergoes distortion to remove the degeneracy by lowering the
symmetry and thus by lowering the energy.
What is electronically degenerate state?
An electronically degenerate state represents the availability of more
than one degenerate orbitals for an electron. In this condition the
degenerate orbitals are asymmetrically occupied.
E.g. In octahedral symmetry, the d1 configuration is said to be
electronically degenerate since three t2g orbitals with same energy are
available for the electron to occupy. In this condition, the degenerate
orbitals are also said to be asymmetrically occupied by electrons.

Whereas the d3 configuration in octahedral geometry is non-


degenerate and symmetric. It is not possible to put two electrons in
one orbital, which is against of Hund's rule of maximum multiplicity.
important is that if the two orbitals of the eg level have different
numbers of electrons, this will lead to J-T distortion. Cu(II)
with its d9 configuration is degenerate and has J-T distortion:
JAHN TELLER DISTORTION : EXPLANTION
the electronically degenerate state, the orbitals are said to be
asymmetrically occupied and get more energy. Therefore the system
tries to get rid of this extra energy by lowering the overall symmetry
of the molecule i.e., undergoing distortion, which is otherwise known
as Jahn Teller distortion.
E.g. In case of octahedral d9 configuration, the last electron may
occupy either dz2 or dx2-y2 orbitals of eg set. If it occupies dz2 orbital,
most of the electron density will be concentrated between the metal
and the two ligands on the z axis. Thus, there will be greater
electrostatic repulsion associated with these ligands than with the
other four on xy plane. This asymmetric distribution of the electron
density may increase the overall energy of the system. To get rid of
this, the complex suffers elongation of bonds on z-axis and thus
lowers the symmetry.
Conversely, occupation of the dx2-y2 orbital would lead to
elongation of bonds along the x and y axes.
• The Jahn Teller distortion is mostly observed in
octahedral environments. Theoretically the electronic
degeneracy in octahedral symmetry is possible in all the
configurations except d3, d8, d10, high spin d5 and low spin
d6 configurations.
However considerable distortions are usually observed in high
spin d4 , low spin d7 and d9 configurations in the octahedral
environment. It is because the Jahn Teller distortion is usually
significant for asymmetrically occupied eg orbitals since they are
directed towards the ligands and the energy gain is considerably
more.

• In case of unevenly occupied t2g orbitals, the Jahn Teller


distortion is very weak since the t2g set does not point
directly at the ligands and therefore the energy gain is
much less.
E.g. d1; d2; low spin d4 & d5; high spin d7 &
d7 configurations.
Because of same reason, the tetrahedral complexes also
do not exhibit Jahn-Teller distortion. Again, in this case
also the ligands are not pointing towards the orbitals
directly and hence there is less stabilization to be gained
upon distortion.
d4 HS
stabilization is
driving force
for distortion

no net change
in energy

tetragonal
elongation
Note: The Jahn-Teller distortion in case of low spin
d8 octahedral systems to give square planar complexes as
explained by some authors is controversial

Jahn-Teller Theorem: electron configurations with unequal


occupancy
of degenerate orbitals are not stable.
d4 HS
Various types of distortions are possible (tetragonal,
trigonal, etc.).
d4 HS
stabilization is
driving force
for distortion.

no net change
in energy

tetragonal
compression
electron configurations with unequal occupancy
of degenerate orbitals are not stable.
d5 HS
Only some complexes can lower their energy by distorting
Square Planar Complexes
Consider a CFT diagram of a tetragonal
elongation taken to its extreme:
Z-OUT & Z-IN JAHN TELLER DISTORTIONS
* The degeneracy of orbitals can be removed by lowering the
symmetry of molecule. This can be achieved by either elongation of
bonds along the z-axis (Z-out distortion) or by shortening the bonds
along the z-axis (Z-in distortion). Thus an octahedrally symmetrical
molecule is distorted to tetragonal geometry.
Z-out distortion: In this case, the energies of d-orbitals with z
factor ( i.e., dz2, dxz, dyz ) are lowered since the bonds along the z-axis
are elongated. This is the most preferred distortion and occurs in most
of the cases, especially when the degeneracy occurs in eg level.
E.g. Usually the octahedral d2, d4 high spin, d7 low spin, d8 low spin
& d9 configurations show the z-out distortion.
Theoretically it is not possible to predict the type of distortion occurs
when the degeneracy occurs in eg level. However it is observed that z-
out distortion is more preferred.
Z-in distortion: In this case the energies of orbitals with z factor
are increased since the bonds along the z-axis are shortened. This
type of distortion is observed in case of octahedral d1 configuration.
The only electron will now occupy the dxy orbital with lower energy.
E.g. The octahedral d1 configurations like Ti(III) in [Ti(H2O)6]3+can
show z-in distortion (theoretically?). In this case, the z-out distortion do
not remove the degeneracy since even after distortion there are still
two degenerate orbitals i.e., dxz and dyz available for the electron to
occupy. See the following diagram.
Also remember that the Jahn-Teller theorem does NOT predict how
large a distortion should occur.
CERTIFICATE

This is to certified that the project work entitled 'JAHN-TELLER


DISTORTION AND IUPAC NOMENCLATURE' is a bonafied
work carried out by ASMITA SINGH , ROLL NO. :- 16CHE013
under the guidance of Dr.SASMITA SAMAL in partial
fulfilment for the award of BSc in chemistry of GOVERNMENT
AUTONOMOUS COLLEGE ROURKELA , PANPOSH during
the year 2016 - 2019 .The project have been approved as it
certifies the academic requirement in respect of project work
prescribed.

Signature of H.O.D Signature of


Dr. SASMITA SAMAL Principle