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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
[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
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]
H2O Aqua
CO Carbonyl
NO Nitrosyl
CH3NH2 Methylamine
C5H5N Pyridine
en
Ethylenediamine
ox2- Oxalato
EDTA4- Ethylenediaminetetraacetato
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:
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:
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.
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
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