WELCOME
FLUXIONALITY
IN
ORGANOMETALLIC
COMPOUNDS
SUBMITTED BY : MANJU
12051023
(4th SEMESTER)
CONTENTS
INTRODUCTION
HISTORY
COMPARISION WITH RESONANCE
&TAUTOMERISM
RATE & TECHNIQUE TO STUDY
INFLUENCE ON NMR-DATA
CLASSIFICATION
NON-RIGID SYSTEMS
INTRODUCTION
Mostly, organometallic compounds possess unique
and well-defined structures. The different atoms of
molecule are in harmonic vibrations about their
mean position.
In alkene complexes of transition metals a molecule
possess more than one thermally accessible
structures.
These structures are interconvertible to each other
rapidly as energy barrier is small between various
forms.
Such behaviour is called fluxionality.
e.g.: Hg(1-C5H5)2
HISTORY
Piper & Wilkinson in 1956 studied fluxional behaviour in
Hg(1-C5H5)2 from its 1H-NMR spectrum which shows a
singlet even in the presence of non-equivalent protons.
In Fe(CO)2(1-C5H5)(5-C5H5), one signal was observed for
-bonded Cp ring.
Similarly, 13C-NMR of Fe(CO)5 shows one signal instead of
two in ratio 2:3 or 1:4 due to trigonal bipyramidal or
square pyramidal geometry.
All these data leads to fluxional behaviour and this name
was suggested by Doering & Roth .
COMPARISION WITH RESONANCE
&TAUTOMERISM
In resonance, the two or more resonating
structures differ only in the position of
electrons but not in the relative position of
atoms.
Also the different structures are less stable
than actual hybrid structure.
But in fluxional molecule, various
interconvertible configurations possess
equal stability.
conti
Sometimes interconversion leads to
two or more non-equivalent
structures having their own
identities. This is tautomerism.
Fluxionality leads to two or more
configurations equivalent in
structure, bonding and energy
content.
RATE OF FLUXIONALITY
AT LOW TEMPERATURE LIMIT:
Consider a two proton system
and their exchange rate are comparable
with NMR time scale.
At this stage, if chemical shift
difference is then
Rate= /2
conti
As we increase the temperature
broadening of signals occurs.
If we measure this initial broadening at
half peak height in units of Hz and
subtract natural line width that was
present before broadening gives W1/2 . In
that case
Rate=(W1/2)
As we continue to warm the sample,
broadening increases and two peaks
collapse.
conti.
AT HIGH TEMPERATURE LIMIT:
At this
temperature, exchange is very fast and we get
a single narrow peak.
Here av is position of averaged resonance at
high temperature limit which is weighted
average of resonance position at low
temperature limit.
av=(naa+nbb)/(na+nb)
Here rate= (av)2/2(W1/2).
TECHNIQUES TO STUDY FLUXIONAL
BEHAVIOUR
Choice of technique depends on rate of
rearrangement.
a) In techniques like Electronic & Vibrational
spectroscopy and Gas phase electron diffraction,
observations get completed in a time 10 -11 sec.
But rearrangement processes do not complete in
this time. Hence fluxional behaviour cannot be
detected by these techniques.
b) NMR technique proves quite useful in study of
fluxionality. By proper choice of temperature
range, rearrangements can be controlled and
signals due to different fluxional species may be
recorded.
INFLUENCE OF RATE PROCESSES ON
NMR DATA
If A & B be two configurations of a nucleus and
they are in equilibrium. na and nb are mole
fractions of A & B, three situations may arise:
a) Slow exchange: We observe two separate signals
at a & b.
b) Fast exchange: Here we get a single peak with
chemical shift and coupling constants are
weighted average of A & B.
av=(naa+nbb)
Jab=naJa+nbJb
c) Intermediate exchange: Here broad bands are
observed.
CLASSIFICATION
Fluxional organometallic compounds may be
divided into six classes:
a) Compounds with acyclic alkenes.
b) Compounds with -bonded cyclic alkenes.
c) Compounds with one or more cyclopolyenes
-bonded or and -bonded to metal atom.
d) Compounds involving rotation of ligands on
metals.
e) Compounds involving ligand scrambling on
metals.
f) Metal carbonyls.
COMPOUNDS WITH ACYCLIC
ALKENES
A large no. of homoleptic and heteroleptic allyl complexes are known.
e.g. Zr(3-C3H5)4
MgBr(3-C3H5)
These may have localised -bonding or
delocalised -bonding.
-allylic group often behave as electron rich
group. Sometimes there is prior dissociation
of one terminal to form a -allyl moiety.
conti
In -allyl moiety there is free rotation
about C-C single bond and therefore
there is exchange of syn and anti
hydrogens.
These species are quite reactive as
there becomes a vacant site on
metal during transformation.
conti
Dynamic behaviour is generally
observed in solutions where the
terminals protons are equivalent on
NMR scale.
e.g.
In CDCl3 at 25C it behaves like
A2B2X system.
But in DMSO at 140C, A4X system is
observed.
COMPOUNDS WITH -BONDED
CYCLIC ALKENES
The iron complex Fe(CO)2(1-C5H5)( 5C5H5) and other similar complexes shows
fluxional behaviour.
At room temperature in 1H NMR two
singlets are observed which is not
expected which leads to a mechanism for
rearrangement reactions which makes
monohapto bonded Cp protons
magnetically equivalent.
NMR spectra of such complexes in
temperature range +30C to -100C gives
POSSIBLE PATHWAYS OF
REARRANGEMENTS
Random Shift
1,2 Metal Shift:
1,3 Metal Shift:
Actually, in this rearrangement 1,2
metal shift is followed.
COMPOUNDS WITH -BONDED
CYCLIC ALKENES
Compounds like Fe(CO)3(4-C8H8), Ru(CO)3(4C8H8), Co(4-C8H8)( 5-C5H5) possess fluxionality.
1H NMR spectrum of Fe complex gives a singlet at
5.2ppm at room temperature.
At -145C two peaks of equal intensity are
observed indicating that eight alkenic protons can
be divided into two groups of four coordinated
and four uncoordinated atoms.
STRUCTURES SUGGESTED ARE
Structure at low temperature was
suggested by Kreiter & co-workers as:
This structure was also supported by X-ray
studies.
Keller &co-workers argued a dynamic
exchange of type:
conti
Cotton suggested a static tub shaped structure
in which coordinated alkenic protons give rise to
high field signal.
Similar is the case for Ru(CO)3(4-C8H8), in which
rate of rearrangement is slow.
Here possible pathways are:
i. Random Shift
ii. 1,2 Shift
iii. 1,3 Shift
iv. 1,4 Shift
. But spectra favours 1,2 shift.
NON-RIGID SYSTEMS
FOUR COORDINATED SYSTEMS:
Fluxional behaviour in such systems
is the inversion of pyramidal
molecules.
In some systems like NH3 and amines
activation energy is in the range 2430kJmol-1 resulting in high rate of
inversion.
But with phosphines, arsines
activation energies are higher than
100kJmol-1 and inversions are slow
conti
In four coordinated systems sq.planar to
tetrahedral fluxional changes are also
common.
FIVE COORDINATED SYSTEMS
Trigonal bipyramidal molecules like PF5 and
Fe(CO)5 shows one peak instead of two in
the ratio 3:2 in 19F and 13C NMR.
This mechanism was suggested by Berry
in 1960 and is known as Berry mechanism
or Pseudorotation.
Here exchange process involves change
SIX COORDINATED SYSTEMS
The octahedral configurations are
generally rigid and hence fluxional &
tautomeric rearrangements do not
occur.
In a few complexes of Fe and Ru of
type MH2(PR3)4 , cis and trans
isomers have well resolved signals at
-50C .
At high temperature these signals
broadens and collapse and at +60C,
REFERENCE
Organometallic Chemistry by R.C.
Mehrotra, A. Singh. Second Edition.
The Organometallic Chemistry of
Transition metals by Robert H.
Crabtree. Fifth Edition. A John Wiley &
Sons INC. Publication.
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