-

CHAPTER -1
 INTRODUCTION

I.I ISOTOPIC EXCHANGE REACTIONS

Isotopic exchange reactions play an important role in radiochemistry.

isotopic exchange is widely used in the radioactive tracer method to study

the identity of chemical bonds, to determine crystal surfaces, to investigate

the structure and chemical composition of compounds, the nature of chemical

bonds and the reactivity of compounds. Isotopic exchange is extensively used

in the synthesis of labelled compounds. The subject of isotopic exchange

reactions was exhaustively studied by ~ a i s s i n s k ~ ' ' ~ ,d w a r d sand

~ ~m~hlett.~

A bibliography,devoted to isotope separation and isotope exchange covering

the published work by Begun and ~ l l e n ~and

, a bibliography of unclassified

references on isotope exchange reactions by Kahn et a ~ . , merit

~ a mention

here. Seaborg 7 has presented a detailed account o f earlier exchange

reactions. Information derived from earliest investigations i n this field was

used t o ascertain whether exchange takes place or not under a set of

conditions and in some cases the experimental data were used to establish

the equivalence or non-equivalence of atoms i n a m o ~ e c u l e . ~~ ~

a u~b e l O

explained the factors affecting the stability of inorganic complexes i n

solution and lability or inertness of complexes towards substitution. Stranks

and wilkinsl ' have summarized the applications of isotopic tracers i n

inorganic chemistry with special reference to exchange reactions i n the study

of both the mechanism of inorganic reactions and the determination of

structure of inorganic molecules. as'^ has given a review on isotope

exchange method of analysis. ~ a i t o l ~ has

' ' ~ reviewed the dynamic properties

of elements, ions and transition metal complexes i n the light of isotopic

exchange reactions. Exchange reactions of group Ill a l k y l derivatives has

been studied by Barry and 3ohn.15 Clark cr dl.,16t17 have described the

relation between the magnetic susceptibil~ty of metal complexes and their

exchange behaviour. Rangamannclr and ~ a i d u " have studied the trend

between magnetic susceptibility and exchange behaviour. A review of

isotopic exchange method of analysis has been presented by 1keda.19 Naidu

and ~ a i d u ~have
' explained the effect of added bases on exchange reactions.

Naidu e t a,1.,21p22 studied the effect of temperature and concentration on

exchange reactions. Kinetics of homogeneous isotope exchange reaction i n

organic phase has been studied by Hradilova and tar^.^) Kostanski and

~ a ~ a have
s ~ ' calculated the energy of activation and activation entropy for

metal complexes by isotopic exchange method.

1.2 NATURE OF EXCHANGE PROCESS

An exchange reaction is defined as a process wherein atoms of a given

element interchange between two or more chemical forms of the element.

The term isotopic exchange reaction is used when an exchange process can

only be detected by isotopic labelling methods. Isotopic exchange reactions

are classified as homogeneous and heterogeneous exchanges depending on

whether the reactants are distributed in the same phase or i n different

phases. The former takes place i n a single phase and the l a t t e r i s

associated with the presence of several phases. The usual f o r r n u ~ a t i o nfor

~~

an exchange reaction is
where X * denotes labelled species. Many exchanges confirm, however, to the

simpler type :

AX + x *- -
4
AX* + x
A, B and X may be singlc citon-15or they rndy bc group of dtoms.
(1.2)

Thus the

exch,it,gc ol r~d~osulphurbctwce~)b0C:I2 slid SC)13r2, wt1ir:h IS r ~ p i d;rt ZO'C,

belongs to the first type with A corresponding to OCIZ, B to OBrZ and X to

S. As an exarnplo of the second type, the alkylhalidr-halide ion exchanges in

alcohol or acetone Indy be cited. lleru A 1s lo be identilled w ~ t halkyl

group and X with halogen.

Exchanges of the type in which a single atom is transferred are known

as atom transfer exchanges. In SO') - S20'3 exchangez5 which occurs by

transfer of the peripheral sulphur atom is an example for this class. A

corresponds to S and X to SOZ3. In principle the reaction could be followed

by labelling any part of X, though not t)y labell~ngA.

1.3 MECHANISM OF ISOTOPE EXCHANGE

The exchange process lnvolves passage through a s t a t e in which the

atoms concerned "forget" their origins and become a randomised pool, from

which the molecules a r e reconstituted according t o pure probability

considerations. Such a pool can be created by dissociation or by association.

(a) Isotopic exchange by dissociation:

If two compounds or two phases of the same compound are subjected

t o electrolytic or thermal dissociation which gives rise to identical particles

containing different isotopes o f a given element, an isotopic exchange

reaction will take place between these compounds or phases. The scheme of

AX -
an exchange reaction through dissociat~onis as follows:
4
A + X

Exchange of halide ~ o n sbetween solid s ~ l v e rhalide and metal halides in

bolution tnay be cited as a11 cxarrlplc.

+
AgBr + ~ a ~ r * ~ g ++ Br- + Na' + ~ r * $
- A ~ B ~+ * NaBr

(b) Isotopic exchange by association:

If two compounds o f a particular element form an associate, an

isotopic exchange reaction takes place between these compounds. The

exchange reaction may be represented schematically as follows:

We may cite as an example of the reactions of this kind, the interchange of

bromine atoms between hydrogen bromide and molecular bromine:

HBr + B r * ~ r H B ~ ~ B ~ ' =H B ~ *t Br2

 The dual dissociation-association mechanism is r e a l i z e d in t h e

inter change of br ornine atoms between lithium bromide and alkyl bromide

according to the following scheme:

LiBr* + R3CBr Li* t Brf- t R3CBr ri5:

[ ~ r *R3CBr 1' + L i t

LiBr + R ~ C B ~ *

(c) lsotopic exchange through other reversible chemical process:

An isotopic exchange redctiol) ~~~volvirrg

d~ssociatiorr and associiitiorr

proceed5 via revcrsiblc r h e r r ~ i c ~r~~ilctio~ib.

l All other reversible chemical

procyuss, 111 whicl~ rnulec-ulch tl.ivi~~t;d ~ l l c r c ~iwtopir

~t c.o~~~l,ositio~i
pilrtic.~p;itc,

also lead to isotopic exchange. An example is the intramolecular exchange of

carbon atoms in rnethylcyclohexane between the side chain and the ring.

As a result of a reversible rearrangement, the radioactive carbon

becomes incorporated into the ring. Exchanges proceeding through reversible

processes may include any interphase exchange, for example, the interchange

of isotopes of mercury between its vapours and liquid, of isotopes of carbon

between gaseous and liquid benzene, etc.

(dl Electron exchange reactions:

The transfer of electrons from the isotopic atoms which are contained

in compounds of a given element in different oxidation states leads to a

redistribution of the isotopes, the atoms being not actually transferred from

one compound into another. This is what occurs with iron compounds in

different oxidation states:

Electron exchange reactions a r e norrniilly studied by labelling the

central metal atorrl of a complex i n one valence state and then measuring

the rate of transfer of the labell~ng isotope to the second valence state. In

special cases ligand exchange can be applied, for instance, in the catalysis by

chrornous ion of the exchange of ~ ~ with

" 0[Cr(H20)6] 3 t which permits

the rate of the cr2' - cr3' electron exchange to be In the

aq aq
example of - the valence states were separated by diffusion,
aq aq'
half-times of upto 39 days were reported2'l whereas when the ferrous ion

was converted to [ ~ e ( d i p y ) ~ l "from which' free ~ e was

~ 'then separated,
Qq
half-times of less than 1 minute were observed at O O C . ~ The
~ rates of

exchange between large symmetrical ions with saturated primary coordination

spheres are frequently very rapid. The outstanding studies concern the

MnOl- -~ ~ [~F ~- ( c N ])3-~

n 0 and - '-
[ F ~ ( c N1) ~ e ~ c h a n ~ e s . ~ ~ , ~ '
 On the basis of mechanisms of isotope exchange reactions given above

we may formulate the following rule: an isotopic exchange reaction proceeds

i n these cases when the exchanging compounds are subjected t o electrolytic

or thermal dissociation i f reversible physicochemical processes or fast

electron transfers takes place between them.

1.4 KINETICS OF lSOTOPE EXCHANGE REACTIONS

When a solution of BX, tagged with radioactive X, is mixed with a

will
solulior~of AX, the l o r ~ ~ ~ c r g r ~ d u ~ l loose
ly the labelled species while the

latter w i l l gain the species, and t h ~ sprocess continues, u n t i l a kinetic

equllibr~um 1s establ~zhed betwrerl the reactants. In ari isotopic exchange

reaction there 1s no net c h e m i c a l r e a c t i o n and hence the o v e r a l l

concentrations of the reactants remain unchanged. However, the entropy of

the exchanging system at equilibrium, wherein a l l the isotopes are uniformly

distributed among the reactants, is greater than entropy of the initial state

I n which the isotopic composition of the reactants is different. The increase

i n the entropy of the system is the entropy of mixing of the isotopes and is
accompanied by a decrease i n free energy. This is the driving force for an

isotopic exchange reaction.

The r a t e c a n be measured e i t h e r by o b s e r v i n g t h e r a t e o f

disappearance of the initially labelled specie; or by following growth or

appearance o f the species i n an initially inactive reactant. The growth or

decline of activity could be ascertained by conventional counting methods

a f t e r separating the reactants. The rate of disappearance of the isotopic

species from initially labelled reactant (0x1 or the rate of appearance i n an

initially unlabelled reactant (AX) is described by a first order rate law and

this was first derived by M C K ~ but

~ ~ it' is fair to point out that earlier

investigations had used equivalent but less general forms of this first order

law. 32133 Subsequently i t has been shown that this first order rate law will

be applicable irrespective of the actual exchange mechanism, the number of

chemically equivalent exchangeable groups, the reactant concentrations, any

d~fiercrlcein isotopic reaction ratca ~ r l t lttic co~~ccritriition

of thc Iabclling

isotope provided trac:er iirnountb arc ~ r r i ~ l o y c d . ~ ~

In a l l tracer investigation., the specific a c t i v i t y 3 5 , the r a t i o o f

counting rate t o unit weight or unit volume or any other function o f

chemical concentration of one of the reactants, is determined as a function

of time. The fraction of exchange, F, at time t, in terms of the specific

dctivity IS given by

Where ' A ~ , 'At and denote the specific activity of fraction A a t time

0, t and oo respectively. If the specific activity of the species A is initially

zero, F becomes

orris^^ proposed a number of useful alternative expressions for the

fraction of exchange. The infinite time value 'Aw , substantially attained

after six t o eight exchange half times have elapsed, is determined from the
specific activity of the initially labelled species BX by the material balance:

For a simple homogeneous system the r a t e R at which the tracer

atoms interchange between two species is given by

where a and b denote t h e concentrations o f the species A X and BX

respectively. The tlrne corresponding to F 2 0.5 is' called half time of

erghange and l t 1s denoted by t i . When t i i~ introduced into the rate

expression it takes the form

R can be determined from the slope of the plot of In (I-F) against t

which is a straight line passing through unity at t=O. More conveniently it

could be determined i n terms of the half time, which'can be read from the

aforesaid plot. R, i n general, i s not a rate constant, but for a given set of

conditions i t becomes a constant. The general methods available i n chemical

kinetics3' are helpful t o deduce the functional dependence of R upon

reactant concentrations. This functional dependence may be determined by

the detailed mechanism of the exchange process. In a simple case the rate

expression can be assumed to be of the general form

where K is the rate constant for the exchange reaction. Ames and
P
willard3' modified first order r a t e equation can be used i n the place o f

McKay's relation, where marked decomposition takes place during exchange,

and hence measurement of Sw becomes difficult.

The reaction is

2.303 a.b
F = ------- . ------- log (St - St)
t atb c
where E represents a constant time interval and is about twice t j .

1.5 COMPLICATIONS 1N THE STUDY OF ISOTOPE EXCHANGE REACTIONS

In the study of isotopic exchange reactions complications can arise

frorn "zero time" exchange or from non-linearity of the In (I-F) against time

plot,

The exchange plots showing the relation between In (I-F) and t

sometimes include zero tlrne exchange and hence depart from the value F-0

when t=O. This may be ascribed t o : (1) Systematic errors in the estimation

of time in fast exchange reaction^^^-^' andlor (2) incomplete separation of

the rea~tants.~'In some cases a zero time exchange can be correlated t o

definite phenomena.31935,43-49 Even i f the incomplete separation or

separation induced effects are reproducible, still estimate can be made of

the rate of the exchange process. In such instances a straight line with the

same slope as that of the plot of In (I-F) and t will be obtained, however,

the straight line does not pass through F:O when t=O.
 Non-linearity of the exchange could be attributed t o elther non-

equivalence of the exchanging atoms in the molecules, or c h e m i c a l

equilibrium not being attained rapidly. In the latter case it may be possible

to get over the non-linearity of the exchange by adjustment of the

conditions.

Tracer isotope rn secular or trarlsierrt radioactive cquil~brium with the

parent 50, radiation induced exchange5' and heterogenityS2 of exchange a r e

some other possible causes of non-lineatity of the exchange plot. The non-

linedr exchange plot can, however be resolved mlo ~ndrvidual llnear parts by

extrapolating back the lirie~rpart of ;lc.tu~I cxc.lrarrgc plot t o irutial tirllc t 0

and substracting these extrapolated values from original curve. The res~dual

curve represents the exchange contribution due to other species. 5 3

1.6 ISOTOPE EFFECTS IN EXCHANGE REACTIONS

In many isotopic exchange studies it is assumed that the reaction rate

of the labelled molecule is identical with that of the "parent" molecule.

Consider the general exchange reaction:

where the superscript* denotes the labelling isotope. There are small

differences in the forward and reverse rates in exchange reactions due to

isotopic differences. These differences can be significant in certain contexts,

especially where the lighter elements are concerned. Both exchange equilibria

and the kinetics of the exchange process are affected.

 The equilibrium constant of the reaction 1.10 is given as:

the quantities (A*/A) and (B*/B) being the specific activities of A and 8. In

most reactions the equilibrium constant should be unity i f no differences in

isotopic reaction rates occur, i.e., a t exchange equilibrium the specific

activities of the A and R moleculrrr specics should be equal. Froni statistical

mechanics, equation 1.1 1 may be written in the form

where the Q f s indicate the total partition functions of the indicated

molecules. The position of equilibrium can be calculated by statistical

mechanics, provided that the relevant vibrational frequencies are known, few

approximations are necessary, and excellent agreement with experiment can

be obtained .
A typical example is

It may be noted that the value of K-1 for the 1 4 ~ / 1 pair

2 ~ is equal to

about twice that for the 1 3 ~ / 1pair.

2~
 Other things being equal, the effects tend to be greatest when one of

the reactants forms strong bonds and the other forms weak bonds or none at

all. The effects also decrease and finally vanish as the temperature raised,

1.7 NON TRACER METHODS IN THE STUDY OF EXCHANGE REACTIONS

Kinetics of exchange reactions are also followed by the method based

on measurement of rate of racemisation, in case of optically active

compounds, and the study of NMR spectra fall under this category.

Optical method:

The loss of optical activity resulting due to molecular events, which

lead to exchange process, forms the basis of the method. However, the

method is useful only in cases where one or both of the reactants a r e

optically active. The rate of racemisation is identified with the rate of

exchange in the method. The use of this method is limited as the rate of

exchange i n certain instances is not identified with the rate of recemisation.

NMR method:

Rates of very rapid exchanges are measured by NMR and ESR spectro-

scopic methods. Measurement of life-times of species in a particular state,

before it makes transition to any other state, forms the basis of the method.

The rate of exchange is then computed from the measured life time. The

rates determined with the aid of the method, in certain cases, compare well

with those obtained by tracer method.

 Techn~quessuch as conductivity, p H measurement and polarography

have also been used i n kinetic studies of coordination compounds. These

studies, like spectral methods, allow continuous examination of the reacting

system which is not usually possible with the methods ~nvolvingchemical

analysis.

1.8 EXCHANGE REACTIONS I N V O L V ~ NMETAL

~ COMPLEXES

a) Types of complexes:

Based on the accessibility to exchange, m e t a l complexes have been

classified into Idbile drld Irlcrt. Conlplexes III which Ilgandb or rr~etalions are

easily replaced by others are called labile complexes. On the other hand,

complexes i n which ligand or metal substitution 1s slow, are termed as inert.

~aube'' classified complexes i n which the substitution occurs i n less than a

minute at 25'C and 0.1 M concentrations as labile. I f a series of compounds

react by identical mechanism with a common reagent, the rate constants are

expected t o be a measure of their relative bond labilities. However, this

assumption i s not universal, slnce the final equilibrium states for the various

reaction systems may differ. Hence, the "degree of attainment" of equili-

brium, as described by Donder and Van ~ ~ s s e l b e r ~ishto

e ~be~ used instead.

Thus a labile molecule may undergo reaction at a slower rate because of the

unfavourable equilibrium position for that reaction. The isotopic exchange

reaction rates do not include this complication, as the heat of reaction for

an exchange process is essentially zero. The equilibrium s t a t e always

corresponds t o random distribution of the labelled atom of species between

the reactants. Hence, the failure to observe exchange, a t least for ligands
is an indication of inert chemical bonds. Kinetics and mechanism of

replacement reactions of coordination compounds have been exhaustively

reviewed by ilk ins.'^

Coordination compounds have been classified as "ionic" or "covalent"

by pauling5' based on the state of electron pairing in the molecules. In

general, it is stated that ionic coniplexes undergo rapid exchange than the

covalent complexes. While it is often the case examples of ionic complexes

can be cited which exhibit relatively slow rates of exchange. This indicates

that other considerations, besides the nature of bonding, play a role in

determining rate of exchange.

~ ~ classified chemical bonds in coordination compounds as

~ u r s t a 1 1has

either "outer orbital" in which the bonds are formed with the use of orbitals

of higher principal quantum number, or the "inner orbital" wherein the

maximum electron pairing occurs with the use of lower quantum number of d

orbitals.

b) Factors influencing the lability of complexes:

The factors which influence the lability or inertness of complex are

the activation energy and structure. Thermodynamic stability of a complex

may not ensure inert character in that a thermodynamically stable species

may readily lend itself for s u b s t i t ~ t i o n . ~ ~ - 6 instances

0 wherein the

differences in energy between the compuund and the activated complexes is

large, the complex displays labile character. The influence of structure on

lability in a complex depends on the electronic configuration of the central

metal atom or ion. For instance, all complexes, i n which the central metal

atom containing electrons i n e orbitals will be labile.

g

Complexes have also been class~f~ed

in more quantitative terms on the

basis of crystal field stabilization energy (CFSE)consideration.61 If the

CFSE of the complex is much larger than that of the activated complex the

compound will react slowly. When the difference is small the reaction will

be rapid. The difference between the CFSE of a compound and that of an

activated complex, derived from the compound influences the r a t e o f

reaction because the change i n CFSE is added to the activation energy of

the process. On the other hand, when the activated complex is less crystal

field stabilized than the compound, the activation energy of the reaction

increases and hence the rate decreases. Further more, calculations based on

CFSE loss showed that when a octahedral compound of d 3 or d 8 type give

rise to square pyramidal activated intermediate, the complex reacts slowly.

However, a l l other high spin complexes are expected t o react rapidly and the

experimental observations have confirmed this view. Similar calculations have

also been made for low spin complexes. All these calculations showed that

the rates of both high and low spin inert complexes dccrease i n the order d 5

> d4 > d8d,3 > d6, the d5, d4 and d 6 systems having low spin confi-

gurations. It is necessary to consider the size and charge of the central

atom and its electron structure while predicting the rates o f substitution

reactions. The lower the charge and greater the size of either the central

atom or the ligand, the more rapid its reactions w i l l be by a dissociation

type of mechanism. In an SN 2 process the smaller the sire and greater the

charge of entering group, the faster the reaction should be for a given
isoelectronic series, the lability decreases with increase in charge of the

central ion.

In generdl, it has buen obarrvud tl\d[ lour coordinate cornplexe~, both

tetrahedral and square planar molecules, react more rapidly when compared

to six coordinated systems which have octahedral geometry. This may be

attributed to the tact that there is enough roorn around the central ion for

the fifth group to enter the coordination sphere in r e s p e c t of four

coordinated complexes. Thus the presence of an additional group would aid

in the release of the original ligand.

The lability or inertness of octahedral complexes has been explained on

the basis of their electronic configuration using the valence bond theory. In

general, the labile complexes are either of the outer orbital type or of the

inner orbital type with at least one vacant d orbital (d2sp3 complexes).

The line of demarcation between labile and inert complexes falls

precisely at the point where all the inner d orbitals become atleast singly

occupied. For example, complexes of MOW) and W(V) are labile, while d3

complexes of Mo(1lI) and W(I11) are inert. Because of their higher positive

charge on the central atom the first two complexes as predicted on

electrostatic grounds alone, would react more slowly by a dissociation

mechanism and not necessarily react more rapidly by a displacement

mechanism.

It is reasonable to assume that all these complexes react by an sN2

mechanism in which the seventh group must be added to the coordination
sphere. Such a process i s greatly aided if an empty lower d orbital is

available to the incoming group. When such an empty d orbital is not

available, the seventh group must be added by using an outer d orbital of

lower stability. This reaction will be slower because of higher activation

energy required.

Outer orbital complexes have the electronic configuration sp3d2 and in

general are labile. For a given isoelectronic series, the lability decreases

with increase in charge of the central ion. Since the outer d orbitals are

less stable than the inner d orbitals, the bonds involving the former are less

stable. Hence, it would be easier lor this c'os~plcxto dissocidte givi~jyrise

to species with roorditiotion nt~rnbi-r livc; ~ r ~ c - colic

. ol thu n ~ ~ b t ~ borbitals
le.

can be Lett out lor hybridization. IlowuvcAr, ds thc positive charge on the

central atom Increases, the bond strength also increases and the compaunds

become inert. The basic assumption in the valence bond theory, that the

coordination bonds in the outer orbital complexes are weaker is completely

unjustified. The bond strengths are very much the same for inner orbital

and outer orbital complexes of a glven type. The other weakness of the

valence bond theory is that it is purely qualitative. Any difference that

exists between dl and d2 systems, or between an inner orbital d3 or d4

system, cannot be predicted with the aid of this theory. Further, all outer

orbital systems are grouped together taking in to consideration only the

charge and size of the central atom, No distinction based on the number of

d electrons is made.

Square planar Pt(ll) complexes have been e x t e n s i v e l y studied.

However, other square planar low spin d8 systems, such as complexes of

Ni(ll), Pd(ll), Au(lll), Rh(I) and Ir(l) have been examined to a lesser extent.

In general, square planar complexes undergo bimolecular nucleophilic

displacement reactions, in contrast to the predominantly d i s s o c i a t i v e

mechanism exhibited by octahedral complexes. Experimental evidence for

SN 2 process is readily available.

Due to both steric and electronic reasons substitution reactions in

these systems proceed mostly by an expansion of coordination number to

accommodate the entering ligand. The metal is exposed for attack above

and below the plane and coordination number greater than four are common.

Furthermore, low spin d8 systems have a vacant pZ orbital of relatively low

energy which can accornrlloddte the pair of elcc.trorr5 d;naled by the entering

ligand. The above postulates receive support from four different kinds of

experimental evidences:

I. Occurrence of substitution with steric retentions.

2. The isolation of many five and six coordinated d 8 systems.

3. Dependence of rate of the reaction on the entering substituent.

4. Steric effects oil rates.

The exchange reactions of coordination compounds can be classified in

terms of mechanism into (i) reversible dissociation of the complex and

(ii) direct bimolecular collision between the reactants.

The two process can be i l l u s t r a t e d for a general octahedral

substitution reaction of the type:

 The dissociative mechanism involves slow rate determining loss of Y to

give a five coordinated intermediate. This is a typical sN1substitution.

The displacement of sN2mechanism takes into account the formation of a

seven coordination in a fast step. These two mechanisms can be differen-

tiated by noting that in a sN1process the important feature is bond

breaking, while SN2 reaction involves the formation of an additional metal-

l~gandbond.

The ligand specificity is also one of the factors which influences the

rate of substitution in coordination rompounds. In general, the substitution

of a ligand is not as drastic as that of a metal atom or a metal ion.

Ligand substitution involves rupture of metal-ligand bonds. However, in a

ligand substitution process the nature and size of the ligand, being replaced,

can influence the rate and mechanism. The rate also depends on whether

(a) substituent present is replaced or not and (b) the entering substituent.

Study of complexes in non-aqueous solvents will reduce some of the

difficulties that arise when water is used a s solvent. ion pairing and

removal of traces of water become more important. Solvent plays a key

role in the reactions of coordination compounds.

1.9 EXCHANGE OF THE CENTRAL METAL ATOM

Metal exchanges are often complicated by interaction of the metal M

with a complex MAn to form all possible intermediate complexes in

concentrations determined by their relevant stability constants. Such

interactions frequently lead to practical difficulties in the separation of the

exchanging species and may be one of the basic causes of the phenomenon of
induced exchange. Duffield and ~ a l v i nperformed
~ ~ one of the earliest

isotopic exchange studies on the exchange of a series of copper chelate

compounds with copper acetate in pyridinc solution. has considered

the relation between bond type and the exchange r a t e of cobalt (11)

complexes of substituted sal~cylaldehydebidentates wrth cobalt acetate in

water and pyridine solutions. Most ol these complexes exhibited magnetic

moments of about 4.5 BM indicating three unpaired electrons in the cobalt(l1)

orbitals. The correspondlrlg outer orbital bonds would be expected to be

labile. l . 0 1 1 ~ observed
~~ the exchange of nickel between pairs of nickel

complexes and pointed out that exchange rate between oppositely charged

complex ions is fast but is slow for like charged ions. This generalization is

of course only applicable to a series of complexes involving a metal atom in

the same electronic state in each complex. Studies of exchange of nickel

with tetra-coordinated nickel ~ o m ~ l e x revealed

e s ~ ~ that
~ ~ ~significant

modifications of the bonding in such complexes can occur in certain solvents,

while certain solid diamagnetic nickel complexes exchange extremely slowly

with nickel chloride in methyl cellosolve at room temperature, other

diamagnetic solid complexes which dissolve in methyl cellosolve or pyridine

with obvious modification of the dsp2 bonding to sp3d2 by coordinatibn

exchange readily. Basolo and h t a t o ~ s hisolated

~~ crystalline compounds of

hexa coordinated nickel(l1) containing two molecules of solvent pyridine. It

was pointed out68969 that thermodynamic stability of chelated complexes for

the first transition series falls i n the order Co < Ni < Cu > h. This order

is not maintained for isotopic exchange rate. The apparently anomalous

position of nickel was then attributed to considerable solvation of nickel

chloride in pyridine. However, the relative stabilities of the planar,

tetrahedral and octahedral configurations of the complex, when solvation is

possible, are probably additional factors determining such an order. It should

be reiterated that there is no priory reason for a correlation between

thermodynamic stability and exchange lability.

The exchange of nickel ion in diamagnetic square planar nickel(I1)

tetraglycine polydentate arnine was studied by Ma et ala70 Kinetic isotopic

exchange studies of metal ion substitution for the system Co(ll) - Co(ll)

EDTA was carried out by Krishnan and 3ervis." Neelakantarn and Jervis72

studied the effect of medium and the mechanism of isotopic exchange of

rare earth metal ions in rare earth EDTA systems. Acid dissociation

corbtant:, of thc yrotorldtcd c:hcl.~tc c.o~liplcxcsof c,criur~~

d n d lutctiurrl with

N-hydroxyethyl EDTA were determined by ~rucher.'~ ~ o t reported

~ n ~ ~the

exchange of nickelous, cobaltous and cupric ions w i t h CDTA complexes.

Thalliurn(lll) exchange studies were carried out by Tsuchimoto and Saito.75

The exchange between bis(d -benzildioximate) nickel(l1) and nickelous ions in

pyridine and pyridine-water media was studied by ~eikotterota.~' Investi-

gations on the isotopic exchange of nickel ions and nickel tetr amet h y lene-

diamine were made by ~ l i a s . ~Homogeneous

~ exchange reaction between

iron(lI1) - 1,2-diaminocyclohexane and j 9 ~ ewas carried out by Loyala and

~ o b u d . ~ ' A mechanistic explanation for the observed rate law and effect of

pyridine on the kinetics of isotopic copper exchange with N-N-ethylene

bis(sa1icylaldimito) copper(l1) ion in chloroform was offered by Elias et ale7'

Larsen and knsen80 investigated the exchange behaviour of trans 1,2-

diarninocyclohexane tetraacetate complexes of magnesium, calcium, strontium

and lanthanum. Kinetics of exchange of lanthanide ions and lanthanide

polyamino polycarboxylate complexes were followed by Glentworth et al,"

Other investigations of lanthanide ion exchanges include those reported by
Asano e t a ~ , , ' ~Brucher and ~ z a r v a s . ~Kinetic
~ study of exchange of cerium

and its ethylene glycol bis(aminoethy1)ether tetraacetate complex was

reported by Wiseall and ~ a l c o m b e . ~ ' Choppin e t al., 85186 studied the

kinetics of exchange of lanthanide amino polycarboxylate complexes with free

lanthanide ions for s e v e r a l different amino polycarboxylate ligands.

Am(lIl)/Eu EDTA exchange reaction and similar Cm(lll), Bk(lll) and Cf(lll)

systems were also investigated by Choppin and ~ i l l ~ a m s ,Hradilova

~ ~ * ~ ~and

staryZ3 investigated the homogeneous isotopic exchange between TI(I) and

TI(II1) diethyldithiocarbarnate in CCI,, and found that the reaction is

bimolecular. Rangarnannar and ~ a r d u ~studied

' the isotoplc exchange rates

of cobalt(1l) in complexes of Co(ll) with phenylenediamine and also

investigated the exchange of Co(ll) in kctoxime Isotope

exchange reaction between As(V) and As(ll1) in acid medium was studied by

Aranikar and ~ e d ~ a o n k a r .Isotopic

~' exchange between 204~1(1)and Tl(111) in

various solvent mixtures were carried out by Cecal and Schneider. 9 2

~ k s t r o mstudied
~ ~ the kinetics of the U(V1) - U(IV) exchange i n perchlorate

and sulphate medium. Exchange of cobaltill) between Co(ll) and dithio-

cyanato bis(thiourea1 Co(ll) was reported by Naidu and ~ a i d u . ~ ' Several

authors studied the exchange behaviour of bis(diethy1dithiocarbamate)

complexes of heavy metal^.^^-^^

Naidu and ~ a i d u ~was

' studied the e f f e c t of bases on the rate of

exchange between Ni(ll) and Ni(xanthate)*. Metal exchange reactions

between divalent metal ions and their dithiocarbamate complexes in dimethyl

sulphoxide were studied by Sachinidis and rant.^^ The exchange of metal

ion, in the Ni(EDTA) square planar complexes i n presence o f aliphatic amine

oximes and cystine have been studied by ~ u r r n a n n " ~ , Libby and

~ar~erum."' Wilkins and ~ i l l i a m s carried

' ~ ~ out the exchange between

~ iand~nickel-phenonthroline
' complex. Metal chelate exchange constants of

bis(diethyldithiocarbamate) nickel(l1) complex in CCI,, were studied by Ruzicka

and tar^,"^ Nyarku and Maddocklo4 investigated the exchange of metal

atoms In b ~ sitquanickel tetritcydno ~iickelatc(ll)tetrahydratc and dececesiurn

hexachloro antimonate(V1 tris(hexachloro)antimonate(lll). Haraguchi and

~reiser"' followed the kinetics and mechanism of metal exchange reaction

of bis(8-mercaptoquinolato)nickel(ll) chelate with copper(l1) ion by an exchange

extraction method. Metal exchange reactions between cobalt(ll) complexes of

polyarninocarboxylic llgands and copper(l1) ions were reported by Mentasti.lo6

Nikitenko e t al.,Io7 observed the kinetics of exchange of americium(ll1)

ethylenediaminetetraacetate w ~ t hcopper(l1) In aqueous solution. Winkler and

w a n n o w i u s l o 8 f o l l o w e d t h e k i n e t i c s o f t h e m e t a l exchange i n

bis(sallcyla1diminato) copper(1l) complexes. Wlnkler and ~ l i a s " ~studied the

isotopic exchange of copper(l1) i n copper chelates with anions of various

bidentate N-phenylsalicyl~ldirni~les
as I~gdnds. Chrorrlium cxchange between

chromium(lll) and benzyl chromium has been investigated by Parris and

~shbrook.'" Edward and ~ s h e r l l lreported the isotope exchange between

hydrated chromium-51(2+) and thiolato pentaaqua chromium(lV) complexes.

They discussed correlation between the effectiveness of thiolato- sulphur as

an electron transfer bridge and sulphur induced trans effects,

Albers and ~ e m a ~studied

" ~ the solid phase radiocobalt exchange

reactions between labelled cobalt chloride and the complexes. The exchange
of 6 0 ~ owith cobalt complexes of salicylaldehyde and substituted salicyl-

aldehyde was found to be 88 per cent i n water and i t was very little in

pyridine and alcohol media. 11 3

1.10 EXCHANGE OF LIGAND

Isotopic exchange reactions in which labelled ligands exchange with

those in the complex can be represented as

Direct ligand substitution by isotopic exchange is most useful in the

estimation of lability of complexes and is of course inaccessible with other

experimental techniques. The exchange of single atom within a ligand was

first studied qualitatively by Anderson et al.,'14 ~ r l e n m e ~ eand

r~'~

pa jaro.'l6 However, ligand exchange with complexes is frequently ' preceded

by aquation in water. Grinberg and ~ikolskaya"~investigated the ligand

exchange rates of series of Pt(ll) complexes. Ligand exchange study of the

salicylaldehyde type quandridentate complexes of nickel:bis(salicyl-

a1doxime)nickel and bis(N-methylsalicylaIdimine)nickel were shown to be

paramagnetic in pyridine solution, owing presumably to formation of an

octahedral adduct incorporating two pyridine solvent mo~ecules.~' These two

complexes exchange rapidly in pyridine with ''I~-labelled salicylaldoxime and

methyl salicylaldoxime, while bis-nickel, which is diamagnetic both as a solid

and in solution does not undergo ligand exchange. Rich and ~ a u b e ~.studied
*
the analogous Au(III) systems. MacDiarrnid and ~ a l l l and
l ~ Adamson e t

observed that the exchange of -CN Jigands i n the tetracyanides of

Pd(ll), h(ll), Ni(1l) and Hg(ll) is extremely rapid. The exchange study also

provided a direct quantitative estimate of the lability of the platinum-

chlorine bond in PtCI3H20- ion but it could not provide a similar estimate

for the ptclU2- ion since the rate constant refers to the process of aquation.

Boyle and ~ a r r i s l attributed

'~ the slower reactions of tetramine species to

strong hydrogen bond~ng 111 the aqua complexes between the unidentate

carbonato ligand and the vicinal aqua ligand to form a relatively stable six-

membered ring,

XU - Co 0
\0 - I-I
/
/

The carbonato ligand in the aqua complexes thus retains i t s bidentate

character and i s less labile to exchange, The very low rate for the

[Cotn2CO3It complex is attributed to steric effects which not only reduce

the probability of direct exchange but also lessen the amount of the complex

existing in the unidentate form. These results must be treated with caution

as '
'0 tracer studies reveal that aquation of these complexes proceeds by
rupture of C-0 bonds as in a decarboxylation r e a ~ t i o n , ' ~ ~ f ~ ~ '
 Kinetic studies of the r a t e o f ligand exchange i n hexacoordinated

complexes i n aqueous solutions revealed that water plays a significant role.

Moreover, the first step i n the ligand exchanges is frequently one of aquation

and i t is desired to ascertain the detailed mechanism of the subseguent

"anation" reaction leading t o the appearance o f a labelled ligand i n the

complex. This anation reaction is often described by a rate law consistent

with either as sN1 or an !iN2

tnechanisrn. Hunt and ~ a u b e ' * i~l l u s t r a t e d

this problem with the help of the reaction

Hunt and planelZ3 studied the exchange of 180 in cr3'

aq
- ~ ~system
' at
~ 0

low salt concentrations (O.05M) i n perchloric acid by precipitating cr3' as

aq
CrP0,,.6H20. E t t l e and ~ o h n s o n investigated
l~~ the exchange of chloride

ligand i n cis- and t r a n ~ - C o ( e n ) ~ C land

~+ c i s - ~ o ( e n ) ~ i ~ ~ w
0 i)t h~ 1free
~+

chloride ion i n aqueous solution. Adarnson et found that the exchange

r a t e o f M ~ ( c N ) ~w~i t-h cyanide ion was f i r s t order i n c o m p l e x i o n

concentration, but independent of free cyanide concentration, pH and ionic

strength.

Kinetics of exchange of thiocyanate i n iron(ll1)-thiocyanate complexes

was studied by Dodgen et Clement et a ~ . , ' ~

reported
~ the synthesis

and ligand exchange studies o f f l u o r o p h o s p h i n e - r h o d i u m complexes.

Chatopadhyay and coetzee12' discussed outer sphere stabilization and other

factors influencing the kinetics of ligand substitution reactions of Ni(ll) and

Co(l1) complexes i n acetonitrile. The polarimetric rates of exchange between

optically active propylenediamine tetraacetic acid and its cadmium complex

were measured in the pH range 4.75-7.00 by Bosnich et a1.128 Grinberg and

~ o r z a k o v a lestablished
~~ the inertness towards exchange of thiourea in

complex irridium salts. The structures of some of the bimolecular oxalate

complexes of were ascertained by studying the oxalate ligand

exchange. Ligar~d exchange 5tudrr.s of tri f luoroinethyl- -dikctonato-

(dimethyl)indium(lll) was reported by Chung and Tuck. 13' The rate of

isotopic exchange of tris aretylacetondto galltu!n(lll) and 14~-acetylacetonein

THF was determined by Chatterjee e t Exchange of acetylacetone

Irgand between gold(lll), gallrurn(lll), tt~dlliurn(lll)and tin(lV) acetylocetonates

and free ligand was investrgated using proton N M R spectroscop~ctechnique by

Geass and ~ o h i a s . ' ~Bryson

~ and ~ l e t c h e r lreported
~~ rate constants,

enthalpies and entropies of activation for reactions occuring a t equilibrium

involving the calcium-EDTA systems. Llgand exchange behaviour of

halopentamtne ruthenium(l1l) cornylexes In aqueous solutions was established by

Tetsuo and ~ a m a d a . ' ~Wajda

~ and ~ o r o l e w i c zstudied
~ ~ ~ the exchange of

oxalate between trioxalato chrornium(lll) and its mixed ligand complexes with

some amino acids to investigate the structure of these complexes. Kinetics

of tetraethylenepentamine ligand exchange reaction of copper(l1) was followed

by James and 0 1 s o n . ' ~ ~ The rate of ligand substitution between tetrakis-

(triethy lphosphite)nickel(O) and cyclohexylisocyanide was studied in n-hexane

and benzene solutions with the aid of infrared spectroscopy by Meier

et Anarora Metoty and ~ o l u c h e n i ~explained

a ~ ~ ~ the isotope exchange

of S in reactive carbon-sulphur compounds using 3 5 ~tracer. Exchange of

thiourea in hexa(thiourea)plumbous nitrate complex has been studied by Naidu

and ~ a i d u . ' ~ O Popplewell and wilkins4' determined the r a t e of

ethylenediarnine exchange with Cu(II), Hg(ll), Nitll) and Zn(1I) complexes.

Khiber et a1.,14' studied the kinetics of exchange of 4-picoline I-oxide

nickel(l1) complexes and found that t h ~rate of ligand exchange in octahedral

Ni(l1) chelate decreases as the substituents and chelate rings kcome more

electronegative. Khodzhaeva and ~ i s s i n 'carried

~ ~ out the isotopic exchange

in diethyldithiocarbamate complexes of some metals with elementary

sulphur[S-351 and the same complexes with tetramethyltiuram disulphide

(TMTD) [ S - 3 5 1 . The exchange reaction between sulphur in diethyldithio-

carbamato ligands and elementary sulphur i n decaline medium proceeds

slowly for the investigated complexes. The exchange reaction between above

mentioned ligands and TMTD in decaline is very fast for the nickel complex,

moderate for the iron complex, and very slow for the cobalt complex. Voss

et reported isotopic ligand exchange of bis(salicylaldiminato) copper(l1)

in tolurnc. Slltyrlirl dud Z,~kl,*rov"~studled tllc ligd\d rxchiinge in solutior~s

of copper(ll1 complexes w ~ t harnines and amino acids. Ligand exchange

studies of cupric diethyldith~ocarbarnateusing electron spin resonance has

been reported by Desai and ~ a 1 d a r . l ~ o~ ~ o l a s h v i l carried

i l ~ ~ out the

ligand exchange kinetics study of simple and mixed complexes of copper(l1)

with glycine and glycylglycine by magnetic relaxation method. The ligand

exchange behaviour of copper(l1) amine complexes with poly(viny1 alcohol) in

aqueous solution was observed by Suzuki et Shtyrlin e t a1.,1"81149

studied simple and mixed ligand copper(l1) fluoride complexes and kinetics of

proton and ligand exchange in solution of copper(l1) complexes with amines

and amino acids. with coworkers examined the ligand

exchange between different dithiocarbamato complexes of some transition

metals. Ligand exchange kinetics of tris(acety1acetonato) chromium(lll) in

acetylacetone has been studied by ~ i d 0 . l ~Kinetics

~ of isotope exchange

between tris(acety1acetone) chromium(ll1) and acetylacetone in propanol has

been carried out by Wajda and ~zemik.'" They have also reported the
isotopic exchange kinetics of tris(ethy1enediamine) chromium(lll) chloride and

ethylenediamine in ~ - m e t h ~ l f o r m a m i d e .Ligand
~ ~ ~ exchange kinetics of

tris(acetylacetonato) chromium(lll) a t elevated temperatures was reported by

Kido and ~ a i t 0 . l ~Ligand

~ exchange in some metal dithiocarbamates has

been studied by Beinrohr and caraj.I5' Kostanski and Magas investigated

the ligand radio isotopic exchange reaction of diethyldithiocarbamato

complexes of R(111), Co(lll), Ni(ll), Cr(lll), Zn(ll) and Cu(ll) in dioxane and

dimethylformamide.24~158

1.1 1 SYNTHESIS BY ISOTOPE EXCHANGE

Isotope exchange is widely used to incorporate radioisotopes into

molecules of the various classes of compounds. For a synthesis to be

accomplished it is sufficient to bring into contact two exchanging substances

and then to separate them. The use of isotope exchange is particularly

important for incorporation of radioactive atoms into complex compounds

which are difficult to obtain by direct chemical synthesis.

I f radioactive atoms are introduced by isotope exchange into a

compound containing several atoms capable of being exchanged, all the

positions become labelled uniformly if the atomic bonds in the molecule are

equivalent and nonuniformly with respect to specific activity if the atomic

bonds are not equivalent. The isotope exchange method does not usually

allow a compound to be labelled at a strictly fixed position, which is

disadvantage. lsotope exchange is extensively employed for preparing

compounds labelled with radioisotopes of the halogens. For example, the

boiling of silver bromide- " ~ r with ethyl bromide gives ethyl bromide- " ~ r :
 Isotope exchange is used to incorporate radioactive sulphur into organic

molecules. Thiourea and its derivatives can be obtained by boiling them with

elementary sulphur-35:

In a number of cases isotopic exchange is one of the steps of direct

chemical synthesis and serves lor preparing an intermediate product. It is

used to deminish the number of steps in chemical synthesis.

 SCOPE OF THE WORK

A survey of the literature pertaining to the isotope exchange studies

indicate that a large number of exchange reactions have been studied by

NMR, ESR and tracer methods. A few systematic attempts have been made

to study the effect of temperature, concentration and added bases on rate

of metal ion substitution. The present investigation is aimed to satisfy the

need in this direction.

The work presented in the thesis deals with isotope exchange reactions

of nickel, copper and chromium complexes. The ligands employed are

diethyldithiocarbamate, resacetophenone oxime and resacetophenone phenyl-

hydrnzone. These ltgands are chohen because 01 their complexing ability.

They are used as inserticides and f~mgicidesin agriculture and they are

biologically active. The metals that are proposed to study, play a

sign~ficant role in enzyme activation.

Isotope exchange react ions of nickel complexes include

bis(diethy1dithiocarbamate) nickel(ll), bis(resacetophenone oximt.) nickcl(l1) and

bis(resacetophenone phenylhydrazone~nickel(l1). Exchange behaviour of

nickel(l1) in these complexes has been studied in the presence of bases.

Bases used were pyridine, 4-picoline and aniline. The experimental results

are analysed in terms of influence of added bases on the lability of the

complexes. The observed smooth exchange has been explained in terms of

modification of metal-ligand bond strength due to adduct formation between

the complex and the added bases. An attempt has been made to explain

the differences in the rate of exchange of metal ion in the presence

of aniline, pyridine and%-picoline. The trend between concentration and rate

of substitution has been discussed. The influence of temperature on reaction

rate has been described.

Rate of substitution of copper(ll) in bis(resacetophenone oxirne)

copper(ll), bis(resacetophenone phenylhydrazone) copper(ll) complexes has been

investigated. The exchange of copper(1i) is studied both in the absence and

in the presence of added bases, aniline and N-methyl aniline. Experimental

observations are discussed on the basis of geometry of the complex, nature

of the metal ligand bond and complex type. The influence of the added

bases on the lability of the complex has been discussed in terms of adduct

formation of the complex with the bases. The difference in isotope

exchange rates in presence of aniline and N-methyl aniline has been

explained with respect to steric effect of methyl group. Effect of

temperature and concentration on the exchange behaviour is examined.

Exchange behaviour of chromium(lll) in tris(diethy1dithiocarbamate)

~Rromium(lll)complex has been studied. The exchange results are analysed

WI the basis of nature of metal-ligand bond and complex type. The trend

ptween concentration and reaction rate has been described. The influence

pt temperature on rate of metal ion substitution has also been discussed.

The work presented in t h e thesis provides information on the

perimental conditions for homogeneous exchange of metal ion in the

mplexes studied. It also gives an idea about the rate of exchange at

ferent temperatures and concentrations, which is useful for the calculation

energy of activation for a particular system.

 REFERENCES

Haissinsky, Me, I. Chim. Phys., 47, 957 (1950).

Haissinsky, M. and Daudel, R., Bull. Soc. Chim., France, 552 (1947).

Edwards, R.R., Ann. Rev. of Nuclear Sci., 1, 301 (1952).

Amphlett, C.B., Quart. Revs., London, 8, 219 (1954).

Begun, C.M. and Allen, R.E., Lsotope Separation and Isotope Exchange,
Technical Information Service, Oak Ridge, Tennessee (1954).

Kahn, M., Applegate, K.R. and Erdal, B., U.S. At. Energy Comm.,
SCR-512, 104 (1962).

Seaborg, G.T., Chem. Revs., 27, 199 (19401,

Juliusburger, F., Topley, 8. and Weiss, I., 3. Chem. Soc., 1295 (1935).

Koskoski, W., Thomas, H. and Fowler, R.D., 3. Amer. Chem, Soc., 63,
2451 (1941).

Taube, H., Chem. Revs., 50, 69 (1952).

Stranks, D.R. and ~ i l k h s ,R.C., ibid, 57, 743 (1957).

Das, H.A., Pap. Sch. Chem. Nucl. Technol., 65 (1977).

Saito, K., Pure. Applied Chem., 38, 325 (1974).

Idem, Cendai Kagaku., 34, 40 (1974).

15. Barry, D.J. and John, O.P., 1. Amer. Chem. Soc., 89, 3970 (1967).
 Clark, H.C., Curtis, N.F. and Odell, A.L., J. Chem. Soc., 63 (1954).

Clark, H.C. and Odell, A.L., ibid, 3435 (1955).

Rangamannar, 0. and Naidu, P.R., J. Inorg. Nucl. Chem., 32, 379

(1972).

Ikeda, M., Kagapu. Sosetusu., 23, 265 (1979).

Naidu, C.R.K. and Naidu, P.R., Acta. Chim. Acad. Sci. Hung., 106(1),
1 (1981).

Munivelu, T. and Naidu, G.R.K., Indian 3. Chern., 24A, 1050 (1 985).

Ramadevi, P., Rao, P.V.V.P., Seshaiah, K. and Naidu, C.R.K.,

3. Radioanal. Nucl. U ~ e m .Lett., 105 (21, 65 (1986).

kirddllovd, E, dr~dStdry, I., Radiochem. Radioanal. Lett., 11, 343

(1972).

Kostanski, M. and Magas, S., Radiochim. Acta., 27, 27 (1980).

McKay, H.A.C., Principles of Radiochemistry, London Butterworthy,

(1971).

Plane, R.A. and Taube, H., 3. Phys. Chem., 56, 33 (1952).

Kierstead, H.A., J. Chern. Phys., IS, 756 (1950).

Silverman, 3. and Dodson, R.W., J. Phys. Chem., 56, 846 (1952).

Deck, C.F., Microfilm Dissert. Abstr., 16, 1578 (1 956).

Sheppard, 3.C. and Wahl, A.C., I. Amer. Chem. Soc., 79, 1020 (1957).

31. McKay, H.A.C., Nature, 192, 997 (1938).

 Hughes, F.J. and Martin, D.S.Jr., 3. Phys. Chem,, 59, 4 10 (1955).

Wilson, J.N. and Dickinson, R.G., 3. Amer. Chem. Soc., 59, 1358
(1937).

Harris, G.M., Trans. Faraday Soc., 47, 716(1951).

Wahl, A.C. and Bonner, N.A., Radioactivity Applied to Chemistry, John

Wiley and Sons, Inc., New York, p.4 (1951).

Norris, T.H., 3. Phys. & Colloid Chem., 54, 777 (1950).

Frost, A.A. and Pearson, R.C., Kinetics and Mechanisms, John Wiley
and Sons, Inc., New York (1953).

Ames, D.P. and Willard, J.E., 3. Amer. Chem. Soc., 73, 164 (1951).

Rona, E.., ibid, 72, 4339 (1950).

Jones, S.S. and Long, F.A., J. Phys. Chem., 56, 25 (1952).

Cinnffarin, E. and Pryor, W.A., 3. A m . Chem. Sac., 86, 3621 (1964).

Rich, R.L. and Taube, H., J. Phys. Chem., 58, 1 (1954).

Harris, G.M. and Stranks, D.R., Trans. Faraday Soc., 48, 137 (1952).

Stranks, D.R., ibid, 51, 505 (1955).

Holden, 3.5. and Harris, G.M., 3. Arner. Chem. Soc., 77, 1934 (1955).

Stranks, D.R., Trans. Faraday Soc., 51, 514 (1955).

Idem, ibid, 51, 524 (1955).

48. Popplewell, D.S. and Wilkins, R.G., 3. Chem. Soc., 4098 (1955).
 Prestwood, R.J. and Wahl, A.C., 3. Amer. Chem. Soc., 70, 880 (1948).

Downs, 3.3. and Johnson, R.E., ibid, 77, 2098 (1955).

Wolfgang, R.L. and Dodson, R.W,, 3. Phys. Chem., 56, 782 (1952).

Wahl A.C. and Bonner, N.A., Radioactivity Apphed t o Chemistry, John

Wiley & Sons, Inc., New York, p. 34 (1951).

Cook, C.M. and Long, F.A., 3. Amer. Chem. Soc., 80, 33 ( 1 958).

Donder, T. De, and Van Rysselberghe, P.J., Thermodynamic Theory of

Affinity, Stanford University Press, Stanford, California, (1936).

Wilkins, H.C., Quart. Revs., 16, 316 (1962).

Pauling, L., The 'Nature of The Chemical Bond, Cornell University

Press, Ithaca, New York, (IY3Y).

Burstall, F.H., 3. Chem. Soc., 173 (1936).

Adamson, A.W., Welker, J.P. and Volpe, M., 3. Amer. Chem. Soc., 72,
4030 (1950).

Adamson, A.W., Welker, J.P. and Wright, W.B., ibid, 73, 4786 (1951).

MacDlarmid, A.C. and Hall, N.F., ibid, 76, 4222 (1924).

Basolo, F. and Pearson, R.G., Mechanism of inorganic Reactions, John

Wiley & Sons, New York, (1958).

Duffield, R.B. and Calvin, M., 3 , Amer. Chem. Soc., 68, 557 (1946).

West, B.O., 3. Chem. Soc., 3115 (1952).

64. Long, F.A., 3. Amer. Chem. Soc., 73, 537 (1951).

65. Hall, N.F. and Willeford, B.R., ibid, 73, 5419 (1951).

66. Johnson, J.E. and Hall, N.F., ibid, 70, 2344 (1948).

67, Basolo, F. and Matoush, W.R., ibid, 75, 5663 (1953).

68. Atkins, D.C. and Garner, C.S., ibid, 74, 3527 (1952).

West, B.O., J. Chem. Soc., 395 (1954).

Ma, N.W.H., White, D.A. and Martin, B., Inorg. Chem., 6, 1632 (1967).

Krishnan, S.S. and Jervis, R.E., 3. Inorg. W 1 . Chem., 29, 87 (1967).

Neelakantam, K. and Jervis, R.E., J. Inorg. Nucl. Chem. Lett., 10, 67

(1974).

Brucher, E., Acta. Chim. Acad. Sci. I.lur\g., 50, 279 ( 1 966).

John, F.W., Disser. Abstr,, 26(10), 5758 (1 966).

Tsuchimoto, M. and Saito, K., 3. Lnorg. Nucl. Chem., 27, 849 (1965).

Reikotterota, N., Bull. Chem. Soc., Japan, CO, 1153 (1967).

Elias, H., Radiochim. Acta, 7(4), 142 ( 1 967).

Loyala, 8.1. and Dobud, V.P., Rev. Real. Acad. Sci., Exactus, Fil.
Natur., Madrid, 42, 231 (1968).

Elias, H., Palewaldt, V.H. and Wonnowius, K.J., Radiochim. Radioanal.

Lett., 11, 341 (1974).

Larsen, N.R. and Jensen, A., Acta. Chern. Scand., Sec. (A), 28, 638
(19741,
Clentworth, P,, Wiseall, 8., Wright, C.L. and Mahamood, A.J., 3. Inorg.
Nucl. Chern., 30, 967 (1968).

Asano, T., Okada, S. and Sakamoto, S., Radioisotopes, 12, 363 (1965).

Brucher, E. and Szarvas, P., Magy. Kern. Foly., 73, 376 0967).

Wiseall, B. and Balcombe, C.I., 3. Inorg. Nucl. Chem., 32, 1751 (1970).

D'olieschlager, W,, Chopp~n, C.R. and Williams, K.R., ibid, 32, 3605
(1970).

D'olieschlagei, W. and Choppin, C.R., ibid, 33, 127 (1971).

Choppin, C.R. and Wllliiims, K.R., ibid, 35, 4255 (1973).

4

Idem, ibid, 36, 1849 ( 1 974).

Rangarnannar, 0. and Naidu, P.R., Indian 3. Chem., 11(6), 600 (1973).

Idem, ibid, 14A, 141 (1 976).

Aranikar, H.J. and Dedgaonkar, V.G., ibid, 15(2), 100 (1977).

Cecal, Al. and Schneider, I.A., J. Inorg. Nucl. Chem. Lett., I q l l ) , 977
(1974).

Ekstrom, A., 3. Inorg. Nucl. Chem., 36, 2355 (1974).

Naidu, C.R.K. and Naidu, P.R. lndian 3. Chem., 18(1), 72 (1979).

Munivelu, T. and Naidu, G.R.K., Acta Ciencia India, XIC No.3, 183
(1 985).

Ramadevi, P., Rao, P.V.V.P., Seshaiah, K. and Naidu, G.R.K.,

J. Radioanal. Nucl. Chern. Lett., 105(5), 309 (1986).
 Chetty, A.N., Rarnadevi, P. and Naidu, C.R.K., ibid, 117(6), 347 (1987).

Naidu, G.R.K. and Naidu, P.R., Acta Ciencia Indica, YIII C, b . 4 , 187
(1982).

Sachinidis, J. and Grant, M.W., Aust. J. Chem., H(10), 2195 (1981).

Murmann, R.K., Inorg. Chem., 2, 1 16 (1 963).

Libby, W.F. and Margerum, D.W., Biochemistry, 4, 619 (1965).

Wilkins, R.G. and Williams, M.J.G., J. Chem. Soc., 4514 (1957).

Ruzicka, J. and Stary, J., Talanta, 15, 505 (1968).

Nyarku, 5. and Maddock, A.G., J. Chem. Soc. Faraday Trans., 78, 2489
(1982).

Haraguchi, K. and Freiser, H., Inorg. Chem., 22(4), 653 (1983).

Mentasti, E., J. Chem. Soc. Dalton Trans., 5, 903 (1984).

Nikitenko, S.I., Martynenko, L.I. and Pechurova, N.I., Zh. Nwrg. Khirn.,
30(5), 1238 (1985).

Winkler, H. and Wannowius, K.J., 2. Phys. Chem., 107(1), 57 (1977).

1

Winkler, H. and Elias, H., Radiochirn. Acta, 24(l), 52 (1977).

Parris, M. and Ashbrook, A.W., Can. J. Chem., 57, 1233 (1979).

Edward, D. and Asher, L.E., 3. Inorg. Nucl. Chem. Lett., 13, 91 (1977).

Albers, D.L. and Lemay, E.Jr.H., I n q . Chem., 13, 940 (1974).

113. Michio, M., Nippon Kagaku Zasshi, 78, (1957).

 son, J.S., James, F.W. and Br~scoe, H.V.A., Nature, 139, 508

ir

f#TErlenmeyer, H. and Lobeck, H., Helv. Chim. Acta., 111, 1213 (1935).

ibh Pajaro, C. and Fava, A., J. Amer. Chem. Soc., 78, 5203 (1956).

@@.
Grinberg, A.A. and N~kolskaya, L.E., a.Rikl. Khim. Lmingr., 24, 893
(1951).

&I&. MacDiarmid, A.G. and Hall, N.F., 3. Amer. Chem. Soc., 75, 5204
(1953).

119, Boyle, J.E. and Harris, G.M., ibid, 80, 782 (1958).

120. Hunt, J.P., Hutenberg, A.C. and Taube, ti., ibid, 74, 268 (1412).

121. Posey, F.A. and Taube, H., ibid, 79, 255 (19571, 75, 4099 (1953).

122. Hunt, J.P. and Taube, H., J. Chem. Phys., 19, 602 (1951).

123. Hunt, J.P. and Plane, R.A., 3. Amer. Chem. Soc., 76, 5960 (1954).

124. Ettle, G.W. and Johnson, C.H., 3. Chem. Soc., 1490 (1939).

125. Dodgen, H.W., Murray, R. and Hunt, I.P., ,Inwg. Chem., 4, 1820 (1965).

126. Clement, D.A., Nixon, 3.F. and Sexton, M.D., 3. Chem. Soc., D. 24,
1509 (1969).

127. Chatopadhyay, P.K. and Coetzee, J.F., Anal. Chem., 46, 2014 (1974).

128. Bosnich, B., Dryer, F.P. and Sargeron, A.M., Aust. J. Chem., 19, 2213
(1966).

129. Grinberg, A.A. and Borzakova, S.S., Zh. k g . Khi

130. Wa jda, S., Bezak, E. and Zarzeczny, A,, Nucleonics, 33, 19 (1974).

131. Chung, H.L. and Tuck, D.C., Can.'J. Chem., 52, 3944 (1974).

132. Chatterjee, C., Matsuzawa, K., Kido, H, and Saito, K., Bull. Chem.
Soc., Japan, 47, 2809 (1974).

133. Geass, G.E. and Tohias, R.S., 3. Organo. Metal Chem., 15, 481 (1968).

134. Bryson, A. and Fletcher, I.S., Aust. .J. Chem., 23, 1091 (1970).

135. Tetsuo, S. and Yarnada, T., Bull. Chcm. Soc., Japan, 45, 3081 (1972).

Wajda, 5. and Horolewicz, M., Bull. Acad. Pol. Sci. Scr. Sci. Chim.,
23, 71 (1975).

James, C.D. and Olson, V.K., Inorg. Chem., 14, 2168 (1975).

Meier, M., Basolo, F. and Pearson, R.G., ibid, 8, 795 (1969).

Anarora Metoty, C.A., Polucheniya, I., Radioktion. Preparatiov, Sb.

Statei., 177 (1960).

Naidu, G.R.K. and Naidu, P.R., 3. Radioanal. Chem., 52(2), 355 (1979).

Khiber, R.W., Thalean, F.L. and Richard, A., Inorg. Chem., 9, 2592
(1 970).

Khodzhaeva, J.V. and Kissin, Y., Zh. Fiz. Khim., 37, 791 (1963).

Voss, H., Wannowius, K.J. and Elias, H., lnorg. Chem., 18(6), 1454
(1979).

Shtyrlin, V.G. and Zakharov, A.V., Koord. Khim., 9(8), 1046 (1983).

145. Desai, K.K. and Haldar, B., Roc. Chem. Symp., 1, 191 (1970).
Gogolashvili, E. L., Deposited Doc., 175, 228 ( 19811.

Suzuki, T., Shirai, H., Tokutake, S. and Hojo, N., P o i y ~ 24(3),

, 335
(1983).

Shtyrlin, V.G., Zdkharov, A.V. and Saprykovil, Z.A., Koord. Khim., M7),
931 (19821,

Shtyrlin, V.G., Zikharov, A.V., Ergenieva, 1.1. and Saprykova, Z.A., a.

Neorg. Khim., 26( 1 I), 2986 ( 1 98 1).

Palazotto, H.C., Duffy, D.J., Edgar, B.L., Que, Jr.1. and Pignolet,
L.H., J. Amer. Chem. Soc., 95, 4537 (1973).

Abrahamson, H., i-leiman, 3.H. and Pignolet, L.H., Inorg. UKrn., 19,
2070 (1975).

Pignolet, L.H., Topics in Current Chemistry, 56, 9 1 ( 1 975).

Kido, Ii., Bull. Chem. Soc., Japan, 53, 82 (1980).

Wajda, S. and Szemik, A., Pol. 3. Chem., 53, 1821 (1979),

Idem, Bull. Acad. Pol. Sci. Ser. Sci. Chim., 28, 125 (1980).

Kido, H. and Salto, K., Inwg. Chern., 16, 397 (1977).

Beinrohr, E. and Cara j, J., Collect. Czech. Chem. Commun., 45, 1785
(1980).

Kostanski, Ma and Magas, S., Bull. Acad. Pol. Sci. Ser. Sci. Chim., 28
423 (1980).