In the strictest

sense, no molecule is absolutely rigid even at absolute temperature

What is Fluxional Molecule?

There are some molecules in which molecular
vibration can convert a molecule from one configuration into another.. Such sort of molecules are called Stereo chemically no rigid molecules Whenever the different configurations of a stereo chemically no rigid molecules are equivalent, they are called Fluxional molecules .. The rate of such type of interconversion is in the range of 102 to 105 S-1 at temperature between +1500 to -1500 c

Distinction Between Polytopal Rearrangement and Fluxionality

A number of stereo chemically non rigid molecules execute a special type of
rearrangement by which they can be interconverted to nonequivalent polyhedral topology. Such sort of rearrangement is called Polytopal RearrangementThat means it is different from Fluxional molecules where different configurations are equivalent. It is normally seen in 4,5 and 8 coordinated system where energy difference between different topologies is comparable .

A classic example is given below- (Allogons) PEtPh2 Br CS2,-780 C Ni Br PEtPh2 Heat Ph2EtP Br

PEtPh2

Ni
Br

Tetrahedral(dark green)paramagnetic

Square planar (dark brown)diamagnetic

FLUXIONALITY OF PF5
PF5 has TBP(trigonal bipyramidal structure) with three F

atoms are in equatorial position and two F atoms are in axial position But in reality these equatorial F atoms are interchanged with two axial F atoms leading to the generation of Fluxionality in the molecule F1 F4

F4
F3 P F5 F2 F5 F3 P

F1
F2

Mechanistic Representation Of Fluxionality In PF5

The Fluxionality of PF5

molecule can be mechanistically explored depicting Berry Pseudo rotation process in which two axial and two equatorial F atoms are interchanged with each other..But one equatorial F atom remains intact in its original position, this group is called pivot group..

Berrys Pseudo Rotation

Spectroscopic Evidence Of Fluxionality In PF5

By Means of 19F NMR Spectroscopy Fluxionality
Qualitative NMR Spectra Of PF5 can be ( At room temperature) Only single intense peak of five equivalent F atoms is observed. This is because of the rapid exchange of position among axial and equatorial F atoms ,they remain practically in equivalent environment even in short timespan of NMR experiment ( At very low temperature) Two peaks with relative intensity of 3:2 are observed. This is due to the fact that at very low temperature the above mentioned rapid exchange of F atoms is seized down resulting two distinct type of environment of F atoms i.e. one axial type(two F atoms) and another equatorial type (three F atoms)

Of PF5 can be monitored..

Structure of XeF6
XeF has total 14 electrons in its Xe centre having six bond pairs and one
6

stereochemically active lonepair.So, from VSEPR theory we expect a pentagonal bipyramidal structure with a lonepair.
But in reality it exist as distorted octahedral structure in solid state, which

is illustrated as [XeF5]+F- with five bond pairs and one lone pair.
In the vapour phase it exist in three different structures.They are

1.Capped trigonal prism 2.Pentagonal bipyramid(lone pair is projected along one corner of basal plane) 3.Capped Octahedron(lone pair is projected along the centre of a trigonal face )

Fluxionality Of XeF6
F F .. F F F F F F F F F F F F .. F F F

..
F

Fluxionality Of Organometallic Compounds

There are variety of organometallic compounds which

shows fluxional behavior..Some of the examples are provided below.

1.Metal Allyl Complexes 2.Fe(CO)2(1-Cp)(5-Cp) 3.Ti(1-Cp)2(5-Cp)2 4.Co(3-C7H7)(5-C5H5) 5.Mo(CO)2(3-C7H7)(5-C5H5)

Fluxional Behavior Of MetalAllyl Complex

Ha H Ha Hb M Hb H
Ha

Ha Hb M Hb

Ha H Hb Ha

M Hb

3-Allyl Complex

1-Allyl Complex

3- Allyl Complex

- Rearrangement Of Allyl Ligand

Spectroscopic Characterization Of Fluxional Metal-Allyl Complex

Fluxionality Of Metal-Allyl complex can be judged by H1

NMR Studies.
(At Room Temperature) one peak Two Doublet total three signals (At 1400 C Temperature)

One peak

One doublet

Total two signals

Fluxionality Of Fe(CO)2(15-Cp) Cp)(

CO H Fe CO

Its Fluxionality can be easily monitored by H-NMR Study.

1

At room temperature two peaks are observed one at 4.4 ppm and another at 5.7 ppm At low temperature a number of signals are obtained between the value of 6.5 to 5.9 ppm

A Mechanistic Overview Of 1,2 Shift in Metal(1-C5H5) system

A detail of 1,2 shift mechanism is depicted belowM

H
M H M H

Fluxionality Of Ti(1-Cp)2(5Cp)2
H

NMR Study reveals At -320c temperature it shows two peaks

H

1H-

Ti

Where as at 62o c temperature it gives only one peak

on

A Special type of FluxionalityMetal Carbonyl Scrambling

Di and poly nuclear metal carbonyl complex shows a

special kind of fluxional behavior in which CO group is scrambled over a skeleton of two or more metal atoms, such kind of Fluxionality is termed Metal carbonyl Scrambling a Classic example is given below

CO

CO

CO

CO

Fe
CO Cis-Form

Fe
CO CO

Fe

Fe

CO Trans-Form

Spectroscopic Detection Of Metal Carbonyl Scrambling

By
1H-NMR

Studies it can be quite convincingly

detected..

At room temperature (280 C)We get one peak At -700 C temperaturewe get two distinct peaks

Special Thank s to Dr. Subrata Bhattacharya