Inorganic rings, Cages and Cluster
Compounds
I M.Sc Chemistry
By
Dr.Karthikeyani.A,
Associate Professor of Chemistry,
Guru Nanak College,
Chennai - 42
Phosphonitrilic polymers are a group of linear or cyclic
compounds containing. structural units of unsaturated –N
=P-linkages. (a) Preparation : The cyclic phosphonitrilic
chlorides and their derivatives are the starting materials for
preparation of various kinds of phosphonitrilic polymers.
Phosphazenes refer to classes of organophosphorus
compounds featuring phosphorus(V) with a double
bond between P and N. One class of phosphazenes
have the formula RN=P(NR2)3. These phosphazenes
are also known as iminophosphoranes and phosphine
imides. They are super bases.
Polyphosphazenes:
Thesecontain more than two P = N – groups. Polymeric
phosphazene dichlorides are formed when further halogen or
halophosphorus substitutions of – NH2 groups in P takes place.
The polymeric phosphazene dichlorides can be represented as
Preparation
Nature of bonding in triphosphazenes
Bonding in phosphazenes is quite interesting.
Diphosphazene contains one P = N and one P – N bonds both of
which are equivalent and the bond length is shorter than single
bond.
This is easily explained by resonance
•In case of trimer and higher phosphazenes however, things
are complex.
•At first sight, there seems to be alternate single and double
bond conjugate systems through out P – N – P skeleton.
•Such conjugate systems are expected to lead to
delocalization of the sort of benzene.
•The cyclic trimer has an accurately planar 6-membered ring
structure but, unlike aromatic systems, it is difficult to reduce
it electrochemically.
•Also, the spectral evidence of delocalized system
(bathochromic ultraviolet shift) is not found. This is explained
As in other phosphazenes, triphosphazenes have
(i)Very stable ring
(ii)All the skeletal interatomic distances are equal if all the six
substituent groups on phosphorus are identical.
(iii)A shorter P – N bond length (~ 158 pm) than single bond
(~177 pm)
(iv)All the nitrogen atoms weakly basic hence protonable (more
so if substituents on Pare electron releasing).
The symmetry of the molecule is like that of benzene.
It has planar structure with three nitrogen and three phosphorus
atoms situated on alternate corners of the hexagon.
The substitutents (X) on P are placed above and below the
plane.
If all the substituents are identical then three of them form
together one plane above and three form one plane below the
molecular plane.
Some more features are mentioned below:
•Nitrogen atoms are sp2 hybridized:
Two such hybrid orbitals are involved in σ -bonding
•Similarly, each phosphorus is sp3 hybridized
Three such hybrid orbitals are involved in σ- bonding.
•There is then one ‘in plane’ π-bonding involving the lone
pair of N (sp2 orbital) in xy plane and the vacant dxy or dx2 –
y2 orbital of the P — atom.
•There are two ‘out of plane’ interactions: (i)Heteromorphic
interactions:
The singly occupied pz1 orbital on the nitrogen overlaps with
the dxzo or dyzO orbital of phosphorus (pπ – dπ bonding).
Homomorphic interactions: There is a pπ – pπ
interaction of pz orbitals of two nitrogens through
the dyz orbital of the phosphorus in between.
•It is believed that the two contributions viz.
heteromorphic and homomorphic are equal.
• This results in separation of the πorbitals into
localized 3-centre orbital islands.
•There are 3 such islands with interruptions at the
three phosphorus atoms. These interruptions in the
M. O’s. prevent the systems from exhibiting
delocalization of the π-electron.
Silicates
Silicates are the minerals
containing silicon and oxygen in
tetrahedral SiO44- units, which are
linked together in several
patterns.
Depending on the way the
tetrahedral units are linked, the
silicates are classified into the
following types.
Silicate Mineral Classification
(based on arrangement of SiO4 tetrahedra)
Silicate Mineral Classification
(based on arrangement of SiO4 tetrahedra)
Nesosilicates Sorosilicates Cyclosilicates
Inosilicates Inosilicates Phyllosilicates
Tectosilicates
