Handout-2

Course 201N
1st Semester 2006-2007
Inorganic Chemistry
Instructor: Jitendra K. Bera

Contents:
1. Molecular Geometry
Resonance
Hybridization and Shapes of Molecule
Fluxionality

1
Resonance
The structures of some compounds and ions cannot be represented by a single formula.
For example, sulfur dioxide (SO2) and nitric acid (HNO3) may each be described by two
equivalent formulas. If only one formula for sulfur dioxide was correct and accurate, then
the double bond to oxygen would be shorter
and stronger than the single bond. Since
experimental evidence indicates that this
molecule is bent (bond angle 120) and has
equal length S-O bonds (1.432 ), a single
formula is inadequate, and the actual structure
resembles an average of the two formulas.
This averaging of electron distribution over
two or more hypothetical contributing
structures (canonical forms) to produce a
hybrid electronic structure is called resonance. Likewise, the structure of nitric acid is
best described as a resonance hybrid of two structures, the double headed arrow being
the unique symbol for resonance.
The above examples represent one extreme in the application of resonance. Here, two
structurally and energetically equivalent electronic structures for a stable compound can
be written. In cases such as these, the electron delocalization described by resonance
enhances the stability of the molecules, and compounds or ions composed of such
molecules often show exceptional stability. There are examples where one canonical
form has a much greater stability than all others. If one canonical form has a much
greater stability than all others, the hybrid will closely resemble it electronically and
energetically. The following factors are important in evaluating the contribution each of
these canonical structures makes to the actual molecule.
1. The number of covalent bonds in a structure: The greater the bonding, the more
important and stable the contributing structure.
2. Formal charge separation: Other factors aside, charge separation decreases the
stability and importance of the contributing structure.
3. Electronegativity of charge bearing atoms and charge density: High charge
density is destabilizing. Positive charge is best accommodated on atoms of low
electronegativity, and negative charge on high electronegative atoms.

Examples: The left hand C=O structure has much greater total bonding than the other
canonical form. In the right hand side structure, the numbers of covalent bonds are less
and the Lewis octet is not
fulfilled for the C. Hence,
the structure on the left is
the most stable one.
Similarly, for the azide
ion, the structure on the
left is the most stable one.

2
Hybridization and shape of the molecules
Hybrid orbital theory assumes that, prior to overlapping, valence orbitals can "hybridize",
or mix, to form a new set of hybrid atomic orbitals that have different spatial
characteristics than the atomic orbitals from which they were derived.

sp hybrid orbitals, formed by mixing one s orbital with one p orbital, leaving two p
orbitals unhybridized. The two new sp hybrid orbitals are 180 apart (linear), and
perpendicular to the two remaining p orbitals.

sp2 hybrid orbitals, formed by mixing one s orbital with two p orbitals, leaving one p
orbital unhybridized. The three new sp2 hybrid orbitals are 120 apart (trigonal), and
perpendicular to the remaining p orbital.

3
sp3 hybrid orbitals, formed by mixing one s orbital with all three p orbitals (leaving no
unhybridized valence orbitals). The four new sp3 hybrid orbitals are 109.5 apart, in a
nonplanar tetrahedral configuration.

sp3d hybrid orbitals, formed by mixing one s orbital with all three p orbitals and one d
orbital. The resulting five sp3d orbitals adopt a trigonal bipyramidal configuration, with
two orbitals pointed 180 apart in an axial configuration, and three in a plane
perpendicular to the first two, 120 apart from each other.

Trigonal bipyramidal s, pz, py, px, dz2 sp3d

4
The overlap of the sp3d hybrid orbitals on P with the 2p orbitals on the F atoms gives five
P-F (sp3d)-2p bonds in two sets: the two axial bonds along the z-axis (180 from each
other) and three equatorial bonds in the xy plane (120 from each other and 90 from
each axial bond). This means that the 5 bonds are not equivalent!
Exactly trigonal or tetrahedral hybridizations are restricted to molecules such as BH3 and
CH4 respectively where all substituents on the central atom are identical. In hybridization
involving nonequivalent hybrid orbitals, such as sp3d, it is usually possible to resolve the
set of hybrid orbitals into subsets of equivalent hybrid orbitals as dp and sp2. The two
linear axial hybrid orbitals make weaker bonds compared to the three equatorial
hybrids. Good examples of the effect of the difference in hybrid bond strengths can be
illustrated with the sp3d hybridization:

Molecules req () rax ()

________________________________________

PF5 1.534 1.577

PCl5 2.02 2.14
SbCl5 2.31 2.43
SF4 1.54 1.64
ClF3 1.598 1.698
BrF3 1.721 1.810

Now, if all the substituents are not identical, i.e., in case of PClxF5-x or similar molecules,
which sites the Cl and F atoms would occupy? It has been experimentally found that
more electronegative substituent occupies the axial site while the less electronegative
substituent occupies the equatorial sites. This is what is called as the Bents rule which
states that More electronegative substituents prefer hybrid orbitals having less s
character and the more electropositive substituents prefer hybrid orbitals having

5
more s character. Although this is an empirical rule it has also been substantiated by
MO calculations.
In case of molecules, AL5 the two structures are TBP and SP. Of the two hybridization
schemes, most of the compounds the trigonal bipyramidal structure. Many coordination
compounds are known, however, with square pyramidal structure. A square pyramidal
arrangement of the hybrid orbitals is formed that involves the sp3d hybrids, but using
different orbitals. However, there are many compounds that cannot be classified readily
into either TBP or SP geometry. There is a continuous spectrum of compounds from TBP
to SP.

Square-based pyramidal s, px, py, pz, dx2-y2 sp3d

Sb(C6H5)5

sp3d2 hybrid orbitals, formed by mixing one s orbital with all three p orbitals and two d
orbitals. The resulting six sp3d2 orbitals are arranged in an octahedral arrangement,
oriented symmetrically along the x, y and z coordinate axes.

Octahedral s, px, py, pz, dx2-y2, dz2 sp3d2

6
VB theory treatment of -bonding: The bonding in ClNO

The overlap of the sp2 hybrid orbitals on N with the 3p orbital on Cl and the 2p orbital on
O give the two bonds and it is the overlap of the left over p orbital on N with the
appropriate orbital on O that forms the (2p-2p) p bond between the two atoms.

The overlap of the sp2 hybrid orbitals on N with the the 2p orbitals on the O give the
three (sp2-2p) bonds and it is the overlap of the left over p orbital on N with the
appropriate orbital on the uncharged O atom that forms the (2p-2p) bond.

7
Energetics of hybridization
A set of hybrid orbitals are constructed by a linear combination of atomic orbitals, the
energy of the resulting hybrids is a weighted average of the participating atomic orbitals.
When C forms 4 covalent bonds, there is a promotional energy from 1s22s22p2
1s22s12p3 which is independent of the hybridization to the valence state. In P atom,
there is little initial promotional energy: the ground state is trivalent as is the valence
state. Any hybridization will cost energy as a filled 3s orbital is raised in energy and half-
filled p orbitals lowered in energy:

3p
Stability increases

sp3
Energy increases

3s

This energy of hybridization is of the order of magnitude of the bond energies and thus
can be important in determining the structure of molecules. We can observe tendency of
some lone pairs to occupy spherical, non-stereochemically active s orbitals rather than
stereochemically active hybrid orbitals. This point can be discussed with two concrete
examples. The bond angles for the hydrides are shown below:

NH3 = 107.2o; PH3 = 93.8o; AsH3 = 91.8o; SbH3 = 91.3o

OH2 = 104.5o; SH2 = 92o; SeH2 = 91o; TeH2 = 89.5o

An energy factor that favors reduction in bond angle is the hybridization discussed above.
It costs about 600 kJ mol-1 to hybridize the central P atom. From the standpoint of this
energy factor alone, the most stable arrangement would be to utilize pure p orbitals for
bonding and letting the lone pair into the pure s orbital. Opposing this tendency is the
repulsion of electrons, both bonding and nonbonding. This will favor an approximately
tetrahedral arrangement of four electron pairs. In case of N and O, the steric effects are
more pronounced because of their small size compared to the other atoms in the
respective series. Therefore, in larger atoms, viz. P, As, Sb, S, Se, Te, the steric effects are
somewhat relaxed allowing reduced hybridization energy of more p character to be
dominant.

8
Fluxionality
Most molecules have a single, well-defined nuclear configuration. The atoms execute
approximately harmonic vibrations about their equilibrium positions, but in other respects
the structures may be considered rigid. There are, however, many cases in which
molecular vibrations or intramolecular rearrangements carry a molecule from one nuclear
configuration into another. When such processes occur at a rate permitting detection by
some physical or chemical means, the molecules are designated as stereochemically non-
rigid. In some cases, the two or more configurations are not chemically equivalent. In
these cases, the process of inter-conversion is called isomerization or tautomerization. In
other cases, the two or more configurations are chemically equivalent and they are called
fluxional molecules. The existence of stereochemical non-rigidity can be revealed by
NMR spectroscopy, since its time-scale is typically in the range 10-2 to 10-5 s. The
rearrangements take place at rate processes with activation energies. When this activation
energy is in the range of 25 to 100 kJ mol-1, the rates of rearrangements can be brought
into the range of 102 to 105 s-1 at temperatures between +150 and 150o C.
Examples: A common type of fluxional behavior is the inversion of pyramidal
molecules. In NH3, the inversion has a very low activation barrier of ~25 kJ mol-1
For PH3, AsH3, the activation barrier is higher. H
H
The 4-coordinate Ni(II) complexes, Ni(R3P)2X2 undergo square N H
planartetrahedral rearrangements with an activation barrier of H N
H
~45 kJ mol-1 and rates of 105 s-1 at room temperature. H

Stereochemical non-rigidity in TBP molecules

The case of PF5
The structure of PF5 has been found to be trigonal bipyramidal. As stated before the
trigonal bipyramidal polyhedron has two distinct sites, the axial site and the equatorial
site. The 19F NMR spectrum of this compound shows a doublet with the separation
between the lines corresponding to the coupling constant J(P-F). However,
for a trigonal bipyramidal structure we anticipate a more complex F(a)
pattern as the axial fluorine atoms belong to one chemically
(e)F
P F(e)
equivalent set and the equatorial fluorines belong to another (e)F
chemically equivalent set. Therefore the spectrum should have been F(a)
more complicated as shown below.

Axial Equatorial

J(P-F) J(P-F)

-J(F-F)- -J(F-F)-

9
Why is only a doublet seen then?
The answer lies in the fact that the molecule is stereochemically non-rigid and is
continuously changing its structure. This is known as fluxional behavior. The mechanism
that accounts for the behavior of PF5 is known as Berry Pseudo Rotation and is shown
below:

In structure 1a the angle F1-P-F2 is 180 and the F3-P-F4 angle is 120. Imagine that that
the former is shrinking and the latter is expanding so that both the angles become nearly
equal and structure 2, a square pyramid, is obtained. If this process is continued further
such that the former F1-P-F2 angle now becomes 120 and the former F3-P-F4 angle
becomes 180 we get the second trigonal bipyramidal structure 1b. Thus in reaching 1b
from 1a through 2, we have essentially exchanged a pair of axial fluorine atoms with a
set of equatorial fluorine atoms without breaking any bonds. In this whole process one P-
F5 does not change. If this process takes place faster than the NMR time scale in the
NMR experiment only one set of fluorines is seen.
For the majority of five-coordinate main-group and transition metal compounds the
energy difference between the trigonal bipyramid (1) and tetragonal pyramid (2)
structures is sufficiently low, so that Berry pseudorotation represents a widespread
mechanism of stereochemical nonrigidity. No angular momentum is generated by this
motion; this is the reason for the term.
Keep in mind that we single out one interchange path here, while in reality all atoms will
rapidly occupy all possible positions in a very dynamic way.
Having bulky substituents such as chlorine or substituents that do not prefer to occupy
axial positions can slow this process down. Accordingly in PCl2F3, although at room
temperature all the fluorine atoms are still equivalent and only a doublet is seen in the
fluorine NMR spectrum, at -143 C the exchange is stopped and one sees two sets of
peaks (a doublet of doublet for the two axial fluorine atoms and a doublet of triplets for
the equatorial fluorine atom).

10
At temperature of 22o C and above, the resonance of F is observed as a single doublet
(31P-19F coupling, 1048 Hz ). However, as the temperature is lowered to 143o C, a
downfield doublet ( -67.4 ) for the axial F atoms and an upfield doublet ( 41.5) for the
equatorial F atom. The single equatorial F atom is further spilt by the two axial F atoms
(2nI+1; n = 2 ; JF-F = 124 Hz) into two triplets. The two axial F atoms is split into doublet
by the single eaquatorial F atom ( 2nI+1; n = 2 ; JF-F = 124 Hz).
Also, the weighted average of the chemical shifts at 143o C {2x(-67.4 ppm) + 1x(41.5
ppm)} is the same as that at 22o C {3 x (-31.1 ppm)} indicating that the structure does
not change on warming even though the F atoms exchanges positions.

11