Double salts are salts containing more than one cation or anion, and are obtained by combination of

two different salts which were crystallized in the same regular ionic lattice

a double salt completely dissociates into simple ions while a complex does not; the complex ion remains
unchanged. For example, KCeF4 is a double salt and gives K+, Ce3+ and F− ions when dissolved in water,
whereas coordination complex when dissolved in water they do not break up completely into individual
ions are called coordination compounds or complexes. e. g. [Cu(NH3)4]SO42+ breaks into [Cu(NH3)4]2+ and
SO42-

Coordination complexes:

- Coordination complex or compound may be defined as a molecular compound that results from
the combination of two or more simple stable molecular compounds and retain its identity in
the solid as well as in dissolved state.
- The hemoglobin in your blood, the chlorophyll in green plants, vitamin B-12, and the catalyst
used in the manufacture of polyethylene all contain coordination compounds.
- Ions of the metals, especially the transition metals, are likely to form complexes. Many of these
compounds are highly colored

- Metal ions that contain partially filled d subshell usually form colored complex ions; ions with
empty d subshell (d0) or with filled d subshells (d10) usually form colorless complexes.
- This figure shows, from left to right, solutions containing [M(H2O)6]n+ ions with M = Sc3+(d0),
Cr3+(d3), Co2+(d7), Ni2+(d8), Cu2+(d9), and Zn2+(d10)
- In most main group element compounds, the valence electrons of the isolated atoms combine
to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of
carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron
leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit
NaCl.
- Transition metals do not normally bond in this fashion. They primarily form coordinate covalent
bonds, a form of the Lewis acid-base interaction in which both of the electrons in the bond are
contributed by a donor (Lewis base) to an electron acceptor (Lewis acid).
- The Lewis acid in coordination complexes, often called a central metal ion (or atom), is often a
transition metal or inner transition metal, although main group elements can also form
coordination compounds.
- The Lewis base donors, called ligands, can be a wide variety of chemicals—atoms, molecules, or
ions. The only requirement is that they have one or more electron pairs, which can be donated
to the central metal.
- Most often, this involves a donor atom with a lone pair of electrons that can form a coordinate
bond to the metal.

-
- (a) Covalent bonds involve the sharing of electrons, and ionic bonds involve the transferring of
electrons associated with each bonding atom, as indicated by the colored electrons.
- (b) However, coordinate covalent bonds involve electrons from a Lewis base being donated to a
metal center. The lone pairs from six water molecules form bonds to the scandium ion to form
an octahedral complex. (Only the donated pairs are shown.)
- The coordination sphere consists of the central metal ion or atom plus its attached ligands.
Brackets in a formula enclose the coordination sphere; species outside the brackets are not part
of the coordination sphere.
- The coordination number of the central metal ion or atom is the number of donor atoms
bonded to it. The coordination number for the silver ion in [Ag(NH3)2]+ is two. For the copper(II)
ion in [CuCl4]2−, the coordination number is four, whereas for the cobalt(II) ion in [Co(H2O)6]2+
the coordination number is six.
- Each of these ligands is monodentate, from the Greek for “one toothed,” meaning that they
connect with the central metal through only one atom. In this case, the number of ligands and
the coordination number are equal.

- The complexes (a) [Ag(NH3)2]+, (b) [Cu(Cl)4]2−, and (c) [Co(H2O)6]2+ have coordination numbers of
two, four, and six, respectively. The geometries of these complexes are: linear, tetrahedral, and
octahedral.
- Many other ligands coordinate to the metal in more complex fashions. Bidentate ligands are
those in which two atoms coordinate to the metal center. For example, ethylenediamine (en,
H2NCH2CH2NH2) contains two nitrogen atoms, each of which has a lone pair and can serve as a
Lewis base
- Both of the atoms can coordinate to a single metal center. In the complex [Co(en)3]3+, there are
three bidentate en ligands, and the coordination number of the cobalt(III) ion is six. The most
 common coordination numbers are two, four, and six, but examples of all coordination numbers
from 1 to 15 are known.

- (a) The ethylenediamine (en) ligand contains two atoms with lone pairs that can coordinate to
the metal center.
- (b) The cobalt(III) complex [Co(en)3]3+ contains three of these ligands, each forming two bonds
to the cobalt ion.
- Any ligand that bonds to a central metal ion by more than one donor atom is a polydentate
ligand (or “many teeth”) because it can bite into the metal center with more than one bond.
- The term chelate (pronounced “KEY-late”) from the Greek for “claw” is also used to describe
this type of interaction. Many polydentate ligands are chelating ligands, and a complex
consisting of one or more of these ligands and a central metal is a chelate.
- A bidentate or polydendentate ligand is known as chelating ligand if on coordination it results
in the formation of a closed or cyclic ring structure. e.g. above structure (b) cobalt complex in
which chelating ligand forms closed or cyclic structures.

- The heme complex in hemoglobin is another important example showed one example of a
chelate
- Polydentate ligands are sometimes identified with prefixes that indicate the number of donor
atoms in the ligand. As we have seen, ligands with one donor atom, such as NH3, Cl−, and H2O,
are monodentate ligands. Ligands with two donor groups are bidentate ligands.
Ethylenediamine, H2NCH2CH2NH2, and the anion of the acid glycine, are
examples of bidentate ligands. Tridentate ligands, tetradentate ligands, pentadentate ligands,
 and hexadentate ligands contain three, four, five, and six donor atoms, respectively. The ligand
in heme is a tetradentate ligand

Isomerism of different coordination complexes.

- The existence of coordination compounds with the same formula but different arrangements of
the ligands was crucial in the development of coordination chemistry. Two or more compounds
with the same formula but different arrangements of the atoms are called isomers.
- Because isomers usually have different physical and chemical properties, it is important to know
which isomer we are dealing with if more than one isomer is possible. As we will see,
coordination compounds exhibit the same types of isomers as organic compounds, as well as
several kinds of isomers that are unique.
- Isomers are compounds with the same molecular formula but different structural formulas and
do not necessarily share similar properties. There are many different classes of isomers, like
stereoisomers, enantiomers, geometrical isomers, etc.
- There are two main forms of isomerism: structural isomerism and stereoisomerism (spatial
isomerism).

Structural Isomers

- Isomers that contain the same number of atoms of each kind but differ in which atoms are
bonded to one another are called structural isomers, which differ in structure or bond
type.
- For inorganic complexes, there are three types of structural isomers: ionization,
coordination and linkage.
- Structural isomers, as their name implies, differ in their structure or bonding, which are
separate from stereoisomers that differ in the spatial arrangement of the ligands are
attached, but still have the bonding properties.
- The different chemical formulas in structural isomers are caused either by a difference in
what ligands are bonded to the central atoms or how the individual ligands are bonded to
the central atoms.
- When determining a structural isomer, need to look at
(1) the ligands that are bonded to the central metal and
(2) which atom of the ligands attach to the central metal.

1. Structural Isomers: Ionization Isomerism

Ionization isomers

- Ionization isomers are identical except for a ligand has exchanging places with an anion
or neutral molecule that was originally outside the coordination complex.
 - The central ion and the other ligands are identical. For example, an octahedral isomer will
have five ligands that are identical, but the sixth will differ. The non-matching ligand in
one compound will be outside of the coordination sphere of the other compound.
- Because the anion or molecule outside the coordination sphere is different, the chemical
properties of these isomers is different.

- Two Ionization isomers. The two isomers differ only which ligands are actually bound to the
center metal. (left) The chloride atom is bound to the cobalt as a chloro- ligand with the bromine
atom as the bromide counter ion. (right) In the other ionization isomer the bromine atom is
acting as a bromo- ligand to the cobalt with the chlorine atom acting as the chloride counter ion.
These two isomers are called pentaamminechlorocobalt(II) bromide (left)
and pentaamminebromocobalt(II) chloride (right)
- The difference between the ionization isomers can be view within the context of the ions
generated when each are dissolved in solution. For example, when pentaamminbromocobalt(II)
chloride is dissolved in water, Cl− ions are generated:
CoBr(NH3)5Cl(s)→CoBr(NH3)+5(aq)+Cl−(aq)
whereas when pentaaquachlorocobalt(II) bromide is dissolved, Br− ions are generated:
CoCl(NH3)5Br(s)→CoCl(NH3)+5(aq)+Br−(aq)

Coordination Isomerism

- Coordination isomerism occurs compounds containing complex anionic and cationic

parts can be thought of as occurring by interchange of some ligands from the cationic part
to the anionic part.
- Hence, there are two complex compounds bound together, one with a negative charge
and the other with a positive charge.
- In coordination isomers, the anion and cation complexes of a coordination compound
exchange one or more ligands. For example,

-
 -

Linkage Isomerism

- Linkage isomerism occurs with ambidentate ligands that are capable of coordinating in
more than one way. The best known cases involve the monodentate ligands: SCN−/NCS−
and NO−2/ONO−.
- The only difference is what atoms the molecular ligands bind to the central ion.
- The ligand(s) must have more than one donor atom, but bind to ion in only one place.
- For example, the (NO−2) ion is a ligand can bind to the central atom through the nitrogen
or the oxygen atom, but cannot bind to the central atom with both oxygen and nitrogen at
once, in which case it would be called a polydentate rather than an ambidentate ligand.

-
- The cationic cobalt complex [Co(NH3)5(NO2)]Cl2 exists in two separable linkage isomers
of the complex ion: (NH3)5(NO2)]2+.
- [Co(ONO)(NH3)5]Cl : the nitrito isomer -O attached
- [Co(NO2)(NH3)5]Cl: the nitro isomer - N attached.

2. Geometric Isomers

- The existence of coordination compounds with the same formula but different
arrangements of the ligands was crucial in the development of coordination chemistry.
- Two or more compounds with the same formula but different arrangements of the atoms
are called isomers.
- Because isomers usually have different physical and chemical properties, it is important
to know which isomer we are dealing with if more than one isomer is possible.
 - Recall that in many cases more than one structure is possible for organic compounds with
the same molecular formula; examples discussed previously include n-butane versus
isobutane and cis-2-butene versus trans-2-butene.
- As we will see, coordination compounds exhibit the same types of isomers as organic
compounds, as well as several kinds of isomers that are unique.

Geometric Isomers: Planar Isomers

- Metal complexes that differ only in which ligands are adjacent to one another (cis) or
directly across from one another (trans) in the coordination sphere of the metal are called
geometrical isomers. They are most important for square planar and octahedral
complexes.
- Because all vertices of a square are equivalent, it does not matter which vertex is
occupied by the ligand B in a square planar MA3B complex; hence only a single
geometrical isomer is possible in this case (and in the analogous MAB3 case). All four
structures shown here are chemically identical because they can be superimposed simply
by rotating the complex in space:

- For an MA2B2 complex, there are two possible isomers: either the A ligands can be
adjacent to one another (cis), in which case the B ligands must also be cis, or the A
ligands can be across from one another (trans), in which case the B ligands must also be
trans. Even though it is possible to draw the cis isomer in four different ways and the
trans isomer in two different ways, all members of each set are chemically equivalent:

- Because there is no way to convert the cis structure to the trans by rotating or flipping the
molecule in space, they are fundamentally different arrangements of atoms in space.
Probably the best-known examples of cis and trans isomers of an MA2B2 square planar
 complex are cis-Pt(NH3)2Cl2, also known as cisplatin, and trans-Pt(NH3)2Cl2, which is
actually toxic rather than therapeutic.

- The anticancer drug cisplatin and its inactive trans isomer. Cisplatin is especially
effective against tumors of the reproductive organs, which primarily affect individuals in
their 20s and were notoriously difficult to cure. For example, after being diagnosed with
metastasized testicular cancer in 1991 and given only a 50% chance of survival, Lance
Armstrong was cured by treatment with cisplatin.
- Square planar complexes that contain symmetrical bidentate ligands, such as [Pt(en)2]2+,
have only one possible structure, in which curved lines linking the two N atoms indicate
the ethylenediamine ligands:

Geometric Isomers: Octahedral Isomers

- Octahedral complexes also exhibit cis and trans isomers. Like square planar complexes,
only one structure is possible for octahedral complexes in which only one ligand is
different from the other five (MA5B).
- Even though we usually draw an octahedron in a way that suggests that the four “in-
plane” ligands are different from the two “axial” ligands, in fact all six vertices of an
octahedron are equivalent.
- Consequently, no matter how we draw an MA5B structure, it can be superimposed on any
other representation simply by rotating the molecule in space.
- Two of the many possible orientations of an MA5B structure are as follows:
- If two ligands in an octahedral complex are different from the other four, giving an
MA4B2 complex, two isomers are possible. The two B ligands can be cis or trans. Cis-
and trans-[Co(NH3)4Cl2]Cl are examples of this type of system:

- Replacing another A ligand by B gives an MA3B3 complex for which there are also two
possible isomers. In one, the three ligands of each kind occupy opposite triangular faces
of the octahedron; this is called the fac isomer (for facial). In the other, the three ligands
of each kind lie on what would be the meridian if the complex were viewed as a sphere;
this is called the mer isomer (for meridional):