Hypervalency

The ability of an atom in a molecular entity to expand its valence shell beyond the

limits of the Lewis octet rule. Hypervalent compounds are common for the second
and subsequent row elements in groups 14–18 of the periodic table. A description of
the hypervalent bonding implies a transfer of the electrons from the central
(hypervalent) atom to the nonbonding molecular orbitals which it forms with (usually
more electronegative) ligands. A typical example of the hypervalent bond is a linear
three-centre, four-electron bond, e.g. that of Fap–P–Fap fragment of PF5.
F

F
P F P
F
H F F
F
F
N F
H
H F
H F F
S
S F
S F F
Cl
Cl F F
F

Hypervalent
What molecule are considered hypervalent and what are not?
 The concept of hypervalency in p block compounds

A hypervalent molecule may be defined as a molecule in which there are more

than four pairs of electrons around the central atom in the conventional Lewis
diagram of the molecule.

J. I Musher in 1969 originally defined hypervalent molecules as those formed by

the nonmetals of groups 15-18 in any of their stable valence states higher than 3,
2, 1, and 0, respectively.

“We refer to these molecules as hypervalent (or HV) since they involve atoms, called
donor atoms, which exceed the number of valences allowed them by the traditional
theory, and thus utilize more electron-pairs of bonding than provide stability in the
Lewis-Langmuir theory. As hypervalent molecules have chemical formulas, and often
the molecular structure, of the addition product of a stable molecule with two
monovalent ligands or a single divalent ligand they could also be called
hypermolecules or “molecules made out of molecules”
 The N-X-L designation

The N-X-L designation is used to describe hypervalent molecules where N is the

number of formally assignable valence electron to the central atom, X is the
symbol of the central atom and L is the number of ligands /substituents directly
bonded to the central atom. The compounds can have coordination numbers from
two to six. All the known compounds of rare gases as central atom come under the
category of hypervalent molecules. Most of the hypervalent compounds have their
structure derived from a trigonal bipyramid or octahedral geometry.

F I F

Xe I F Dicordinate

F I F
10-Xe-2 10-I-2 10-F-2
F3C
Cl F O
F3C

I F Cl
Br Tricoordinate

Cl F F3C O
10-I-3 10-Cl-3 CF3 10-Br-3
 CF3
F F F3C
O O
F
S Xe
F O P
F K
Tetracoordinate
F
O
10-S-4 14-Xe-4 10-P-4
CF3 F3C
CF3
F F3C
O OPh
F
P F PhO Pentacoordinate
F P CH2Ph P OPh
PhO
F
O OPh
10-P-5 F3C 10-P-5 10-P-5
CF3
F O
2
O
F F Ph
O Si
S O
Ph Ph
F F O O Hexacoordinate
Te
F Ph Ph 2Na
12-S-6 Ph 12Te-6 12-Si-6
 Explaining Hypervalency

Pauling’s expanded octet model

Through promotion of electrons into vacant high lying d orbitals

leading to sp3d/sp3d2 hybridizations

It has been shown by many theoretical researchers that even if d

orbitals are necessary to provide quantitative bond energies in
hypervalent species these orbitals have occupancies of only 0.3
electrons at the most .

In 2013 it was calculated that for XeF2 the Valence bond structures corresponding to
the sp3d hybridization model account for only 11.2% of the wavefunction and brings
in only stabilization energy of only 7.2 kcal/mol much less than the total binding
energy (64.1 kcal/mol)

The discovery of F3- which has a structure same as that of I3- has been one of the biggest
deathblows to the use of d orbitals in explaining the structure of hypervalent molecules
as conventionally the central atom of I3 – was assumed to have a trigonal bypyramid sp3d
geometry while the same fails for F3- since fluorine being a first row p block element is
expected not to have d orbitals for invoking hybridization.
 The three centre 4 electron (3c-4e) model

Proposed in 1951 by Pimental and Rundle

In a three centre 4 electron molecular system three atoms or fragments each

contribute a single atomic orbital from which one can construct a set of three
molecular orbitals (MO’s) of bonding non bonding and antibonding character

For example in the case of XeF2, three pure pz orbitals combine to form a set of
MO’s of which only the first two are occupied giving a net bond order of 0.5.
 The Xe−F bonds result from the combination of a filled p orbital in the central
atom (Xe) with two half-filled p orbitals on the axial atoms (F), resulting in a
filled bonding orbital, a filled non-bonding orbital, and an
empty antibonding orbital. The two lower energy MO's are doubly occupied.
The bond order for each Xe-F bonds is 1/2, since the only bonding orbital is
delocalized over the two Xe-F bonds. A similar bonding can be envisaged for
I3.

In the case of the trigonal bypyramid PF5, the three shorter equatorial bonds
(153.4 pm) are described by localized orbitals formed by 2 center 2 electron
bonds. The longer axial bonds (157.7 pm) can be described by the three
molecular orbitals formed by a single p orbital on phosphorus and a p orbital
on each of the fluorines. The two electrons in the non bonding orbitals are
localized on the fluorine atoms and do not contribute to the bonding and the
bonding is due to the two electrons in the bonding orbital and therefore each
axial P-F bond is effectively a half bond.
VB treatment
Linus Pauling

For hypervalent compounds in which the ligands are more electronegative than the

central, hypervalent atom, resonance structures can be drawn with no more than four
covalent electron pair bonds and completed with ionic bonds to obey the octet rule.
For example, in phosphorus pentafluoride (PF5), five resonance structures can be
generated each with four covalent bonds and one ionic bond with greater weight in
the structures placing ionic character in the axial bonds, thus satisfying the octet rule
and explaining both the observed trigonal bipyramidal molecular geometry and the
fact that the axial bond length (158 pm) is longer than the equatorial (154 pm).

For a hexacoordinate molecule such as sulfur hexafluoride, each of the six bonds is the
same length. The rationalization described above can be applied to generate 15 resonance
structures each with four covalent bonds and two ionic bonds, such that the ionic
character is distributed equally across each of the sulfur-fluorine bonds.
 The modern view of stable hypervalent molecules- charge shift bonding

Bonds in which the covalent-ionic resonance energy is the

major cause for bonding have been termed charge shift bonds

XeF2 m.p.140 C
The high stability of XeF2 indicated by its large atomization energy cannot be
ascribed to any of its individual VB structures but mostly from an exceptionally
large resonance energy arising from the mixing of several VB structures which
are covalent and ionic.

XeF2 = F Xe+F F Xe+ F F Xe2+ F

This model also supports that electron must be transferred from the
central atom to the ligand for hypervalency to take place. Also stresses the
importance of low ionization energies for the central atom and high
electron affinity for the ligands. Therefore charge shift bonding along with
the 3c 4e model can explain the higher stability of hypervalent molecules
such as XeF2
P block compound and Earlier explanation Modern explanation supported by
its property suggested based of theoretical studies where d orbitals
participation of empty d are not used.
orbitals
PF5 Assuming promotion of Invoking 3c-4e bonding of the axial
F electrons to vacant higher bonds: wavefunctions described as
F
P F
energy d orbitals resulting in superpositions of resonance structures
F
sp3d hybridization. some of which obey the octet rule
F (ionic) and some break the octet rule
(covalent).
SF6 Assuming promotion of Invoking two 3c-4e bonds involving
F electrons to vacant higher delocalization of one of the two bonding
F F energy d orbitals resulting in pairs on to the substituents and
S sp3d2 hybridization resulting in a charge distribution of +1
F F
F
on the central atom and -0.5 on each of
the substituents
XeF2 Sp3d hybridization with 3 centre 4 electron bonding along with
structure and unusual equatorial positions of the charge shift bonding.
stability trigonal bypyramid occupied Extra stability due to charge shift
by lone pairs bonding (Bonds in which the covalent-
F
I ionic resonance energy is the major
Xe I
cause for bonding )
I
F
Phosphine oxide, sulfur Covalent compounds Covalent bonds but not involving d
dioxide having p- d bonds orbitals. The back bonding of electron
R resulting in shorter P-O density to the * acceptor orbitals of
P O S
and S-O bonds phosphors or sulfur which are the
R
O O LUMO. An example of negative
hyperconjugation effect (n to *)
R

No explanation possible 3 center - 4 electron bonding

F
based on d orbitals since
F fluorine , a first row p
block element has no d
F
orbitals
General lack of Absence of d orbitals of Higher electro negativity of the first row
hypervalency among the lower energy p block elements and smaller size of
first row p block these elements
elements
H3SiOSiH3 and N(SiH3)3 p- d bonds between VSEPR rules are applicable only if
structures have large silicon and substituents have higher or comparable
bond angles around oxygen/nitrogen reduces electronegativity as the central atom.
oxygen/nitrogen, effect of lone pair on Large bond angles are due to weak
structures not predicted geometry pairing of electrons on oxygen as a
by VSEPR rules result of weakly electronegative SiH3
group as well as electrostatic repulsions
between bulky SiH3 groups.
 Primary factors stabilizing a hypervalent bond: Electronegative substituents
F
Cl

PhI + Cl2 Ph I Xe + F2 Xe

Cl F
F
F
R3P + MoF6 R
R P F
Ph2SiF2 + F Ph Si
R
Ph
F
F
F

(CF3)2S + F2 CF3
S
CF3
F

Electronegative groups stabilizes hypervalent bonds in main group compounds

Apicophilicity: Tendency of a substituent to prefer axial poisitions in TBP

Experimentally observed apicophilicity of selected substituents in TBP:

F > CF3 > OR/OH  Cl > NMe2 > Ph > Me

The apicophilicity of a substituent mainly depends on its electronegativity, but some

other factors can also have an effect. A bulky substituent prefers equatorial positions,
which are more distant from other substituents. A substituent with π-bonding ability
also prefers equatorial positions.
 Primary factors stabilizing a hypervalent bond: Steric constraints on small rings
OR
OR
O P
O Small rings (5-6 mem) prefer
(RO)3P + OR
O axial/equatorial orientation
O than eq-eq or ax-ax.

O F
HOCH2CH2OH O
(RO)3SiR Na+ R Si F
NaOH Si
O Me
N
Ph F3C CF3 Me
F3C
CF3 Me
Strategic choice of
O O
substituents can even
S S overcome the apicophilicity
preference of electronegative
O O substituents

CF3 Small rings impart

F3C Ph F3C CF3
stability to molecules
H2O H2O, H+
unlike their acyclic
reflux
analogues
Ph2SO + HOC(CF3)2Ph No reaction
 Primary factors stabilizing a hypervalent bond: Polydentate ligands

An Atrane is a tricyclic molecule with three five-membered rings having mostly P or

Si as central atom. It has a transannular dative bond by a nitrogen atom

Silatranes exhibit unusual properties as well as biological activity in which the

coordination of nitrogen to silane plays an important role. Some derivatives such
as phenylsilatrane are highly toxic. The transannular coordinate bond in atranes can be
stretched by controlling their stereoelectronic properties. Proazaphosphatrane,
obtained from azaphosphatrane is a very strong non-ionic base and is utilized as an
efficient catalyst.
 Primary factors stabilizing a hypervalent bond: Polydentate ligands; Porphyrins

Tetravalent
hexacoordinate

Pentavalent
A hypervalent phosphorus(V) porphyrin with axially bonded
hexacoordinate
azobenzene groups functions as a molecular photoswitch.
describe the luminescent on–off behavior of an interesting
metalloid porphyrin-based photoswitch they prepared using the
axial-bonding capability of hexacoordinated phosphorus(V)
porphyrin. The trick was to irradiate 1, inducing E–Z
isomerization of the azobenzene group to simulate an on–off
switch.
Unique aspects of structure and reactivity of hypervalent compounds

Apicophilicity
Site exchange- fluxionality: pseduorotation
Stable intermediates of reaction
Increased reactivity
Stabilization of low oxidation states of p block
compounds

Experimentally observed apicophilicity of selected substituents in TBP:

F > CF3 > OR/OH  Cl > NMe2 > Ph > Me
 Site exchange- Fluxionality: Stereochemical non-rigidity

Fluxional molecules are molecules that undergo dynamics such that some or all of

their atoms interchange between symmetry-equivalent positions.
Berry Pseudorotation Pentacoordinate
Turnstile Rotation
Bailar Twist Hexacoordinate chiral
Ray-Dutt Twist
Ring whizzing Organometallic Cp complexes
In hypervalent pentacoordinate molecules, two types of bonds exist. These bonds may
interconvert by an isomerization process without breaking of bonds.
In Berry Pseudorotation (Proposed by R Stephen Berry , Univ of Michigan 1960) the axial
bonds of a TBP become equatorial and two equatorial bonds become axial- the whole
process possibly through a square pyramidal intermediate situation. Although it was first
proposed by Berry for PF5, this scrambling activity is too fast for PF5 to be followed up by
even low temp. NMR spectral studies. When one or two fluorines are replace by chlorines,
it becomes possible to monitor this process by Variable Temp NMR.

Turnstile rotation is more complex involving he simultaneous internal rotation

of one axial and one equatorial bonds followed by other bonds rearranging.
 Stereochemically non-rigid structures: Berry Pseudorotation

In NMR if a spin active nucleus couples with another spin active nucleus, each with
a spin quantum number I, then 2nI+1 lines will be seen where n is the number of
NMR active nuclei in the vicinity.
Spin quantum number I of 19F, 31P, 1H and 13C are ½ while for 35Cl it is 3/2.

2nI+1; n= 2 gives triplet n=1 gives doublet

For PCl2F3 one observes that in the fluorine NMR spectra taken at room temperature
there is only one kind of fluorine’s but when measured at -143°C one gets two sets of
peaks (a doublet of a doublet for the two axial fluorine’s and a doublet of a triplet for the
equatorial fluorine at -143 °C). This shows that the axial and equatorial fluorine’s are
exchanging positions at room temperature faster than the NMR technique can follow. One
envisages the intermediate situation as a square pyramidal structure as shown. This
process which does not involve bond breaking is called Berry pseudorotation

A1
A1 E3 A
E3 1
E3
E1 A E1 A E1 A
E2 E2 E2 A2
A2 A2
Berry Pseduorotation JP-F 1048 Hz

at 22 °C
F
JP-F 1048 Hz Cl P
F
1048 Hz
Cl
F

124 Hz JF-F 124 Hz

-67.4 ppm + 41.5 ppm

at 143 °C
 60 °C

For ClF3, Berry

F
pseudorotation is arrested
60 °C below -60 C and a similar
Cl F
spectra is obtained
F

4 ppm 116 ppm

23 °C

For SF4, Berry

pseudorotation is arrested
F below -100 C and a
100 °C spectra with equal splitting
F S
F of axial and equatorial
F 79.9 Hz fluorines are obtained

90 ppm 35 ppm

 Hypervalent compounds as stable intermediates 
Hydrolysis of tetravalent chlorosilanes

In the reaction mechanism proposed for the hydrolysis of trichlorosilane,

there is a pre-rate determining nucleophilic attack of the tetracoordinated
silane by the nucleophile (or water) resulting in a hypervalent
pentacoordinated silane. This is followed by a nucleophilic attack of the
intermediate by water in a rate determining step leading to a
hexacoordinated species ( transition state) that quickly decomposes giving
the hydroxysilane.
 Increased reactivity of hypervalent species in comparison to
normal analogues

Si Si
F F
F F

2 H2O 2 H2O
24 hrs 15 minutes

No hydrolysis Hydrolysis

Silane hydrolysis was further investigated by Holmes and coworkers  in which

tetracoordinated Mes2SiF2 (Mes = mesityl) and pentacoordinated Mes2SiF3- were
both reacted with two equivalents of water. Following twenty-four hours, almost
no hydrolysis of the tetracoordinated silane was observed, while the
pentacoordinated silane was completely hydrolyzed after fifteen minutes. This
indicates increased reactivity of the hypervalent species
 Stabilizing unusually low oxidation states of main group elements

Anthony J Arduengo ( first stable NHC fame) designed and prepared a stable
P(I) compound by using a specially designed ligand which by covalent and
coordinate bonds formed a 10-P-3 system. The presence of two lone pairs on
the phosphorus was also proved by using it as a ligand to bind two metal
sites simultaneously.
N

O P O

10-P-3

O Mn(5-Cp)(CO)2
O
2 Mn(5-Cp)(CO)2
N P
N P
THF Mn(5-Cp)(CO)2
O
O