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From the time of Werner*1 *» 1B03, the whealstry wf
aetal eoaplexee has aade such a rapid advance and has
feuad application in so aany Iivereified fields that it
is difficult to keep paee with the day to day aevelopaents
which are being added to its existing vast and enormous
ehealcal literature. Moreover the chemistry of complex
c^mpoun'8 doss not csaae to exist slaply with the asntioa
of reaotions of metnls with coordinating end ehelating
agents, having nitrogen or oxygen and even sulphur or phos
phorous m donor atoms, but finds new outlstw in structural
problems t> be solved by highly complicated theories eased
en quantum theory and quantum aechanioe and by ueing extrenely
refined physical tools like T.R, W.H.R., S.S.R#f U.f
and Raman spectra t x-ray, magnetic euseeptlbllity, aass
8peotroso> yt electron microscopy st. And then beyond this,
it exhibits Its ia*my pec«lt»r yet highly faneinating facets
ia anslyttoal chsmlstry beginning with precipitates ia
estimating astals in voluaetrio analysis and eolorlaetry
es indicator ©omplexes, finally finding support for their
identity an4 stability in various electro-eheaieal aethods,
eg, pH aetry, polarography, eoul>aetry, saperoaetry etc.
and modern analytical techaiquee like equilibrium ditlysls,
radio lsotopy, liouid-ll^niia extraction , ion exchange,
chromatogr phy. ete.
Tet there Is another aspeot of ths problem, vis.,
the type of motels which show readiness to undergo
chelation or complex Ion formation. It is ween that most
Of the investIgstlons on complexes have bean limited to
the metels of transition series. Complexes of nontraawltion
elements so far investig«ted are quite small
in drawer and reactive of analytical import-nee (usually
weawd on colour changes) have only ween etudled with dyes
(substituted and unwubaUtutcd), pigments, s fsw amines
and aalo-otsaplexea. As such there exists enough scops for
investigatlag new ooaplexing and chelating agents which
amy be specific for non-tranaitlon elements. To one such
class of reagents belong the anils which though not well
reoognlssd aw chelating agents, are known for exhibiting a
resonating structure when brought in contact with different
Lewis acids. Study with these compounds can, therefore,
fora a new b^sls of study In the field of co-ordination
onanistry.
Before introducing the subject on the interaction
Wf aetala with anile and its derlvatlvee, it will not he
ut of place If a brief survey of the chealetry of -nils,
Lswia acids and of ths different physic-chemical techniques
employed to study complexes la a»ds.
AHILS
Anils arw organic compounds obtained by condensing
3
eroaetie aldwhydws with wiwaatlw a-sinee, Tawy arw
represented by a foraula RR'C - H- RM . Where R way
he em alkyl, aryl or hydrogen attached to wn imino
carbon or aitrogwn. They are often referred as Sohifffo
(2) bases after the none of the dieeoverer, Sehiff (18S4)V
A aechPTiiwm rega ding their preparation apy be givea
belowi
> C « 0 ♦ HfWRw
• <i •" • i in
R»
OH
1 - C «• I *» L
> 0 • H - Rf* ♦ %0
Tha rwactio i is acid oatalyawd an* is generally carried
out by refluxing the carboayl eosipouad an^ the anlne with
aa aaeotroplc agent, like sine chloride, If accessary.
Anile show HitIs or no tendency to polymeria? spontan
eously but any be polymerised by heat and acids. For
•sample, wwawjalealllawt O^Rr-CR » *%%, Is resinlfied
on heating with aqueoue hydrochloric eeid or formic
awid<3).
Xoarea wnd Mignonaw*4* oyathesised various enils
by the action of an aryl Orlgaard reagent with an aryl
cyanide. Mont ague at el^8* leter found thafc certain
4
aailldsB, which aey be regarded as ^-hydroxy lmines,
react with alkyl or aryl Orlgnarde to give the corres
ponding lalaws in «*bout 40"/ yields.
Hitter wae the first to dshydrogsnats amines to
give lalaww' '. He found that isobomyl aniline ie
readily dehydrogenoted with eulpher at $?19Q t give an
yiwld of about 89 Jf of the anil of oertphor* |
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