This article was downloaded by: [University of Cambridge]On: 11 November 2014, At: 04:48Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number:1072954 Registered office: Mortimer House, 37-41 Mortimer Street,London W1T 3JH, UK

Synthesis and Reactivity inInorganic and Metal-OrganicChemistryPublication details, including instructions forauthors and subscription information:http://www.tandfonline.com/loi/lsrt19

Oxo-Cation Complexes -Part XIII. Dioxouranium(VI),Oxovanadium(IV) andOxovanadiuti(V) Complexesof the Schiff Base (N,N′-2,2′-bis(aminoethyl)methylamine-bis(3-carboxysalicylideneimine))Kamalendu Dey a , Asoke Kumar Sinha Roy a ,Alok Kumar Mallick a & Kartik Kumar Nandi aa Department of Chemistry , University ofKalyani , Kalyani, 741 235, IndiaPublished online: 22 Nov 2011.

To cite this article: Kamalendu Dey , Asoke Kumar Sinha Roy , Alok Kumar Mallick& Kartik Kumar Nandi (1992) Oxo-Cation Complexes - Part XIII. Dioxouranium(VI),Oxovanadium(IV) and Oxovanadiuti(V) Complexes of the Schiff Base (N,N′-2,2′-bis(aminoethyl)methylamine-bis(3-carboxysalicylideneimine)), Synthesis andReactivity in Inorganic and Metal-Organic Chemistry, 22:2-3, 145-159, DOI:10.1080/00945719208021378

To link to this article: http://dx.doi.org/10.1080/00945719208021378

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SYNTH. REACT. INORG. MET.-ORG. CHEM., 2 2 ( 2 & 3 ) , 1 4 5 - 1 5 9 ( 1 9 9 2 )

0x0-CATION -m,zxss - PART XIII.

DIOXOIr3A':IUFT('v'I), OXOVLNADTJT( IV) 4 ,: O ~ O V A N 4 D I I J ? ? ( V ) C P P E X E S 0;. THE

SCFI?? BAS? (N,N1-2, 2'-BIS( UlINOC1HuL)!~T'YLA'I~~-~~S( 3-CAWOMSALICYLI-

D V T I T " 1%) )

Kamalendu DeyX, Asoke Kumar Sinha %y, Alok Kumar Mall ick

ar,d K a r t i k Kumar Nandi

'lepartment of Chemistry, Univers i ty of Kalyani , Kalyani - 7'41 235,India .

4ESTRACT

A ne.3. Sch if f base ( N , N -2,2' -b 1 s( am inoe thy1)nethylam ine-bis

( 3 - c a r h o x y s a l i c y l i d e n e ~ ~ e ) ) , abbreviated t3 Hqfsadien, h a s been

synthes ized f ?om 3-formylsal icyl ic ac id (H2f sa) ane die thylene t r iamine

( d i e n ) . The c h e l a t e s of t h i s l igand with UO:', V02+ and V03+ have a l s o

been synthesized and charac te r ized i:ith t h e h e l p of e lementa l a n a l y s i s ,

m o l a r conductance, n a p e t i c s u s c e p t i b i l i t y and v i s i b l e - W and 12

sue c t roscopie s.

II\T 3O?UCT I O N

3 - F o m y l s a l i c y l i c a c i d (H2fse) , and i t s Schi f f bases \;it- mono-

and d i - m i n e s a r e v e r s a t i l e l igands (F ig . 1 anc! 2 ) and t h e i r conplexes

wi th t r a n s i t i o n and non-tr?nsit.ion meta ls have been e x t e n s i v e l y s tud ied

i n r e c e n t years'-".

such a s d ie thylene t r iamine ( d i e n ) , t r i e t h y l e n e t e t r a n i n e ( t r i e n ) , e t c . ,

have not been much used a s l igands f o r complex foxmation. We have

Hc*,*ever, Schi f f bases of H2fsa with oolyvnines,

145

Copyright 0 1992 by Marcel Dekker. Inc

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146 DEY ET AL.

H C C- OH I I ' I 1 N OH 0 '

R

R=CHs,Et.Ph, -CHI -COOH

etc.

FIG. 1

therefore studied the

II I1 N OH 0

H

/

R \

N

H ,yJ- OH

FIG 2

C-OH II

C I1

H \

N OH 0 /

H 2C I

H2C, NH

HzC, N OH 0 I I I I I

H' c+Yc-OH kJ F I G . 3

( HGfsodien 1

t r a n s i t i o n and non-transition metal complexes

of Schiff bases derived from H2fsa with polyamines.

descr ibes the synthesis and charac te r i sa t ion of a new ?:?.iff base

( t i ,N'-2,Z1-bis( aminoethyl) methylmine-bis( 3-carboxysalicylideneimine)

derived from HZfsa anc? dien abbreviated t o H4fsadien) (Fig 3) and i t s

che la t e s with UO$ V02+ and V03+.

EXPERMENPAL

This paper

?ea;rent grade chemicals and solvents were used, an? they were

pu r i f i ed and dried whenever necessary by standard methods.

Data f o r charac te r i sa t ion of the new cmplexes were co l lec ted a s described ?reviously 11,12.

The Schiff base l i - a n ? , Hqfsadien was i so la ted i n the solid

s t a t e by t r ea t ing dien 0.02 rnol wi th H2fsa 0.04 mol in refluxing

m t h a n o l (200 ml) i n 65% yie ld , m.p. 208-21O0C(dec.).

0x0-cation complexes reported i n t h i s note, however, i so l a t ed

following an in-situ reaction procedure.

Most of the

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0x0-CATION COMPLEXES. XI11 147

Preparation of metal cauplexes

- /-(Hqfsadien)U02(N03)+7 (2) - H2fsa (4 m o l , 0.664 g) was dissolved in ethanol (15 ml) t o

which d i m ( 2 mmol, 0.226 g) i n ethanol (5 ml) was added dropwise while

s t i r r i n g . The mixture turned yellow and was heated under reflux on a

s t e m bath f o r 30 m i n .

6H20 was then added t o t h i s ho t solution of the lie;and, Hqfsadien while

s t i r r i n g .

1 h.

f i l t e r e d o f f , washed with ethanol and dried i n vacuo. Yield 80%.

An ethanol so lu t ion containing 2 mmol U02(1;03)2.

The whole mixture was then heated under gent le reflux f o r

During reflux a yellow compound was separated out , which was

The complex (2) is soluble i n W S O but insoluble in a l l other

ccmnon orEanic solvents. Rwever, it is appreciably soluble i n ho t

water. The canpound is diamagnetic.

- /-( H2f sadien)U0&7H20, (2)

Reaction of the d i sod im s a l t of the above Schiff base,

Na Y fsadien (prepared in-situ as described above, by the reaction of

H2fsa, deta and NaOH) with U02C12 ( 2 mmol; 0.682 g) in ethanol (70 ml)

gave t h i s yellow product i n about 75% yie ld .

ethanol and dried in a desiccator over fused CaC12.

2 2

It was washed with

The complex is soluble i n LMSO, but insoluble in other common

organic solvents. It is diamagnetic.

The complex ( a ) , when t rea ted with s t o i c h i m e t r i c mount of

NaOH i n aaueous ethanol, gave compound (2). - r ( H q f sadien)V0-7SOq, (2)

This d i r t y yellow compound was prepared by a method s h i l z r t o

th2 t employed for (A) us- a hot e thanol ic solution of V03Ob.H20(2 mmol;

0.362 g). It was washed with ethanol and dried i n vacuo. Yield a&.

Thz cmplex is highly soluble i n MSO, p a r t i a l l y so i n ho t water,

but insoluble i n othor organic solvents. It is paramagnetic ( P e f r =

1.67 B.M. a t room temp.).

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148 DEY ET AL.

- r ( H 2 f sadien)VO-mpO, (5) This grey yellow compound was prepared by a method s imi l a r t o

t h a t employed f o r (2) us- solid VO(CH3COO), ( 2 m o i , 0.37 g ) it

was washed with ethanol and dried in a desiccator over fused CaC12.

Y i e l d 75%.

The complex i s highly soluble in ITIS0 and moderately so in CMF.

It is paramagnetic ( Feff = 1.6s B.M. a t room temp.).

r ( H 2 f sadien)VO_f, ( 5 ) A suspension of Hqfsadien (2 -01, 0.8 g) i n ethanol (30 m l ) was

t r e a t e d v i t h a so lu t ion (18 r n l ) of sodium hydroxide (4 mmol, 0.16 g)

i n water-ethanol (3:5, v:v) mixture and heated on water bath for few

minutes t o ge t a yellow so lu t ion of t he sodium s a l t of the ligand.

Solid VO(CH3C02)2 ( 2 mmol; 0.37 g) w a s then aCdea t o t h i s so lu t ion

and then refluxed on a water bath f o r 30 min.

compound separated out. It was recrys ta l l ized from MF-EtOH mixture.

Yield 70%. MSO, LMF and dioxan and is parmagnet ic (

temp.).

while a grey granular

The complex (5) is hygroscopic. It is soluble in hot

= 1.70 B.M. a t room F e f f

The enhydrous canplex (2) can also be obtained from (i) on

keeping it is a vacuum des icca tor over conc. H2S04 for about a week.

r( Na2fsadien)V0-7, < 8) A suspension of Hqfsadien ( 2 mmol, 0.8 g) in alcohol (30 ml)

was t r ea t ed with a so lu t ion (18 ml) of so.’im hydroxide (4 m o l ,

0.16 g) i n water-ethanol (3:5, v:v) mixture and heated on water

bath f o r f e w m i n s . t o ge t a c l e a r yellow so lu t ion of t h e sod im s a l t

of the l igand.

( 2 mmol, 0.36 g) was added t o the r e su l t i ng so lu t ion a t the room

tem?erature while a voluminous brown compound separated out, f i l t e r e d

and washed with aqueous ethanol.

A c l e a r ethanol so lu t ion containing VOS04.H20

Yield 70%.

The complex is soluble i n water and a l so in coordinating

solvents. It is paramagnetic ( Peff = 1.73 a.br. at room temp.).

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0x0-CATION COMPLEXES. XIII 149

(!:a2fsadien)VO(OH), (2) p____._- ~

H2fsa ( I r mmol, 0.664 g) was d isso lved i n e thanol (15 ml) t o

which

while s t i r r i n g . The mixture turned yellow and was heated under

r e f l u x on steambath f o r about 20 a i n . T o t h e hot s o l u t i o n of t h e

l iyand Hqfsadien, sodium hy-’roxide ( 2 mmol, 0.08 g ) i n water - e t h a - o l (3:5, v/v) mixture was added t o make t h e r e a c t i o n mixture

a l k a l i n e (pF 9 ) . An e t h a n o l i c s o l u t i o n containing 2 mmol V03O4.H20

was t h e n aaded and the r c a c t i o n mixture wzs ref luxe2 f o r 1 h. A

d i r t y yellow conpound .hich was i s o l a t e < by f i l t r a t i o n was washed

(2 mmol, 0.206 g) i n e t h a n o l ( 5 ml) was added dropwise

e t h a n o l ane d r i e d i n vacuo. Yield 7m.

The complex i s s o l u b l e i n wzter and a l s o in csord ina t ing

so lvec ts . It i s diamagnetic.

RFXETS AND DISCUSSION

Synthes is . Depending on t h e r e a c t i o n conc‘itions t h e l izand

Hqfsadien r e a c t s with t h e salts of dioxo-uranium(V1) and oxo-

vmadium( IT!) i o n s a f f o r d i n e d i f f e r e n t 0x0-cation complexes. The

chemical composition of t h e i s o l a t e d complexes depend t o s m e e x t e n t

on t h e n a t u r e of t h e r e a c t a n t s , s o l v e n t s , t h e pH of t h e s o l u t i o n s

and t h e o t h e r condition:. of t h e r e a c t i o n s .

1) support t h e i r formulat ions.

E l e n e n t a l ana lyses (Table

Magnetic moments. A l l t h e 0x0-vanadium( IV) c m p l e x e s (2, 2, 2 anc $) are paramagnetic, t h e p e f f v a l u e s being in t h e range 1.67 - 1.73 B . M . , which a r e q u i t e c l o s e t o s p i n only value f o r one unpaired

e l e c t r o n a s is expected f o r 0x0-vanadium(1V) che la tes . These

approxim?tely normal mzpnetic moment v a l u e s i n d i c a t e t h a t t h e r e is no

s i g n i f i c a n t i n t e r a c t i o n between neighbouring vanadium( I V ) i o n s . On t h e o t h e r hand, t h e complex (2) is diamagnetic a t room temperature,

i n e i c a t i n g t h - t it c o n t a i n s 0x0-vanadim(V) species . The uranyl

complexes ( a ) and (2) a r e diamagnetic (Table 1) a s is expected f o r

t h e s e i o n s having do c o n f i g w a t i o n

10,11

10,ll

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TABL

E 1.

Ele

men

tal

an

aly

sis,

mag

pet ic

mom

ents

, co

lou

r an

d m

elti

ng

po

ints

of

som

e di

oxou

rani

um(V

I),

oxov

anad

ium

( Iv

) P*

(v)

com

plex

es.

Cm

ple

xa

Foun

d (C

alc.

) %

Iv

lngn

etic

m

omen

t beff

C

olou

r M

N C

H Na

(B .M. ) -

at

room t

emp.

-.

<..

" D

iam

agne

tic

[(H4f

sa

dien

)UO

J-b

Yel

low

30.9

8.7

29.8

2.4

-

I(

H2f

sad

ien)

U0,

+7H

20,

(2)

Yel

low

35.9

5.9

35.6

2.0

- (30.01)

(8.8)

(30.26)

(2.6)

(NO3)29 (2)

(34.74)

(6.13) (35.03)

(3.06)

[(H4fsadien)V0-7SOq,C(J)

Dirt

y 9.5

7.9

41.9

4.1

- ye

llow

(9

.06

) (7.47) (42.7)

(3.7)

r(H

2fsa

dien

)VO

-7H

20,

(9)

Gre

y 10,l

8.9

50.2

4.7

- [(

H2f

sadi

en)V

0-7,

(5)

Snuf

f 10

.5

9.8

51.0

3.8

- r(

Na2

fsad

ien

)VO

-7,

(6)

Brow

n 10.8

8.4

47.7

4.0

8.0

1.73

[(N

a2f

sadi

en)V

O( OH-7, (

I)

Dir

ty

8.9

8.2

46.0

3.2

9.0

Dia

mag

neti

c

yell

ow

(10.56)

(8.7)

(49.8)

(4.35)

(10.97)

(9.05) (51.7)

(4.09)

(10.3)

(8.2

) (47.24)

(3.34)

(9.05)

yell

ow

(9.7)

(8.0)

(45.7)

(3.4

) (8.76)

u 1.67

1.68

1.70

a)

The

com

poun

ds d

id n

ot m

elt

up

to 30O0C.

b)

emp

iric

al f

orm

ula

of

(I) C

2&1UN5014

c)

emp

iric

al f

orm

ula

of

(2)

c~~H~,vN~o,~s

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0x0-CATION COMPLEXES. XI11 151

Molar conductance v a l u e s . The molar conductance value of t h e

complex (2) i n l3:SO i s 45.7 ohm-’ cm2 mol-I i n d i c a t i n g t h a t t h e

complex i s a 1:l e l e c t r o l j j e 1 3 .

on t h e o t n e r hand, a r e non-conducting i n t h e same so lvent (Arq = 5.8 - 8.2 ohm” c m 2 mol-I range).

conductance values of t h e rest of t h e compounds could not be recorded.

I t is i n t e r e s t i n g t o r o t e t h a t t h e value o f A , ( i n I X S O s o l u t i o n ) of

t h e complex (1) - i n c r e a s e s on prolonged s tandine , which a f t e r about 3

days a t t a i n s a value of 58.5 ohm-’ a n 2 mol‘ . sed bv t h e fol lowing equat ion, which shows t h e f o n ? t i o n of a 1:2

e l e c t r o l y t e in s o l u t i o n :

U02(H4L)(N03)2 + LT:SO = rUO2(H4L)(WSO)X-7*+ + 2 NO;

- r w h e r e H4L s tands f o r H4fsadien-7

The complexes (l), ( z ) , (5) and (2).

Due t o s o l u b i l i t y problems t h e molar

1 T h i s nay be r a t i o n a l i -

E l e c t r o n i c spectra. The e l e c t r o n i c s p e c t r a of t h e oxovan.-dim( IV)

and 0x0-vanadium(V) complexes a r e re?orted in Table 2. The ox+

vanadium(1V) complexes, (3 ) t o ($) snow one prominent maximimum at about

15500-16000 cm-’.

ap?ear i n t h e s9ec t ra a t

I n addi t ion , a few shoulders ( o r weak-broad bands)

11000-13000 cm” and 17600-18800 cm-’.

Although t h e e l e c t r o n i c s p e c t r a of t h e oxo-vanadium( I V ) conplexes

are discussed in many place^^^^^, t h e ass iennent of observed,

e l e c t r o n i c absorpt ion bands f o r 0x0-vanadium( N) complexes h a s been a

m a t t e r of controversy, Kost of t h e d iscuns ions ere made i n terms of

CbV and a few i n t e r n s of CZv symmetry.

t r a n s i t i o n s 21-e expected for t h e d’ oxo-vanadium(IV)20.

of t h e symmetry from C4,, t o Ca o r Cs h a s t h e e f f e c t of removing t h e

degeneracy in the d - o r b i t a l s and t h u s f o u r t r a n s i t i o n s are predicted.

I n symmety t h r e e e l e c t r o n i c

The lowering

It has been observed i n t h e p r e s e n t i n v e s t i g a t i o n t h a t a l l the

bands a r e not w e l l resolved i n t o t h e i r components. The broad band

observed about 15500-16000 cm” is e a s i l y i d e n t i f i e d , and may be

a t t r i b u t e d t o 4 *B, i n CkV symmetry 16’20.

range 17600-18800 an” may be due t o

The high i n t e n s i t y of t h i s band may be due t o inf luence of some charge-

The shoulder in t h e

4 2A, t r a n s i t i o n ( i n C4v).

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152 DEY ET AL.

TABLE - 2 .

E l e c t r o n i c abscjrption s p e c t r a l d a t a of oxovanadium complexes with

Hqfsadien.

complex/Ligand Solvent $,, in Cm-I

H4fsa dien Nu j o l mull 27397( s h ) ; 24390; 22727; 21 276.

26500 sh * 24937 23000t shj ’ 1 8 W f sh) , 16000, IlbCO(w).

26315 sh ) , 24390, 1‘7857 w) , 155OO( w) , 13908 I b r , v ) , 12500(w).

25641 25000( s h ) , 188001 sh), 17300, 15500(w, br) , I ’ l ~ ( w > .

25641 23255( sh) 19000( s h l , l8000[ sh) , 15OOO(sh., 12500 w,br).

sh = shoulder ; w = w e a k ; b r , w = broad and weak.

16 t r a n s f e r or i n t r a - l i g i n d t r a n s i t i o n . The low-energy band observed

around 11000-13000 cm” may be assigned t o ‘?j2 j % t r a n s i t i o n s .

t h e p r e s e n t oxc-vanadium( IV) complexes of t h e l igand H4f sadien a r e

square p:iramidal i n s t r u c t u r e l i k e t h o s e of oxo-vanadium(N) complexes

o f / -diketones, t h e y shoula then r e a d i l y add a donor l i g a n d t o t h e

metal a t t h e vacant axi.1 coord ina t ion p o s i t i o n and thereby produce a

marked s h i f t t h e d-d t r a n s i t i o n bands. The e l e c t r o n i c s p e c t r a of t h e

p r e s e n t complexes have been found t o be so lvent independent r c o m p a r a b l e

s p e c t r a were obta ined when measured rn pyr id ine and INSO as seen i n

n u j o l mull (Table 2)-7,

of t h e present complexes (2) t o (g) may be due t o s t e r i c hindrance of

If

This so lvent independent e l e c t r o n i c s p e c t r a

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0x0-CATION COMPLEXES. XI11

O H H O I

o= c 0 I c = o

153

FIG. L

t h e t r i a n i n e fragment of t h e che la te ring, whizh might put a b a r r i e r

t o c l o s e ap?roach of t h e donor solvent o r e l s e t h e complex may have a

t r igonal -b ipyr imida l s t r u c t u r e which, unl ike t h e square-pyramidal

geometry, h inders complex-base i n t e r a c t i o n . A l t e r n a t i v e l y , it nay

so happer, t h a t i n t h e s e complexes t h e secondary amide (-1JH) func t ion

might from a weak bond with t h e vanadium atom ( s e e Fig. 4) and t h u s

Drevent t h e incoming donor l igand from forming a bond.

16

The absorp t ion bands observed f o r t h e present 0x0-vanedium(V)

However, t h e band around c m p l e x (2) are very d i f f i c u l t t o ass ign .

17000-18000 an’’ may be due t o ligand-to-metal charge t r a n s f e r

t r a n s i t i o n . It i s q u i t e i n t e r e s t i n s t o note t h a t t h i s diamagnetic

0x0-vanadium(V) canplex (z) may be converted t o t h e paramagnetic

oxc-vanadiun(N) complex (5) simply by gr inding it b!ith sodium

b i s u l p h i t e in a l i t t l e water . The s p e c t r a l p a t t e r n and Sand p o s i t i o n s

(in t h e range 350-450 nm) of t h e free l igand Hqfsadien d i f f e r

apprec iab ly from those observed f o r t h e 0x0-cation complexes of

u r a n i m and vanadium.

21

Infrared spec t ra . The genera l t r e n d of the i n f r a r e d s p e c t r a

of t h e present oxo-cation complexes a r e comparable with t h o s e

publ i shed previously with s i m i l a r tvpes of ligand1’2’22-24. A l l t h e

0x0-cation complexes under discuss ion show broad-medium bands in t h e

reg ion 3600-3000 an-’, which a r e ass ignable t o OH s t r e t c h i n g v i b r a t i o n s

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154 DEY ET AL.

TABLE 3.

Infrared spec t ra l data of dioxo-uraziunl( V I ) , 0x0-vanadium( N & V) . Complexes with S c k i f f bases.

Complex/Ligand Band ( cm" )

- rH4f sa dien-7

[(H2fsa dien)U0&7, ($1

r ( H 2 f sa dien)V0-7H20, (5)

3660-3350( br,rn), 3?ibO(w), 3140-28800

3640-3240(br, band not w e l l resolved) ; 3200-2960 br,w); 2410-2300(w,br w i t h two peaks!; 1645( s), 1595( s); 1545(m, with a sh a t 1520); 1450(br, m ) ; 1355(m); 1305(w ; 1275(vw), 125O(s with sh a t I Z O O ] ; 1155(s); 11OO(vwj; 1080(vw); 920(br,m with sh a t 875); 830 vw); 79O(vw); 665(s 650 w ; 6 2 0 1 ~ ) ; 58O(vw) ; ~ ~ O ( V W ] i 425tm1.

3640-2800[br. not well resolved):

900 br, rn with &I ?t 875(vw); 790(sh); 765tm); 650(w); 62O(w); 420(br,w).

3640-2800(br); 2300(m); 1645, 1600 & 1555 3 str. bands not well resolved); 1450 {str. bands with sh a t 1460). 1390(w); 1305(w); 127O(w); 123O(sj;

3600-3200(br, not wel l resolved); 3030(w ; 291O(w); 2840(w); 1640(rn); 1600(w{ ; 1570-1500 ( o r , m not well resolved wi th several peaks) ; 1440(br, m with sh e t 1468); 1400(br, w); 129O(w); 1245(m)* 1200 vw); 1150(m); 1080(vw); 1035(vwj; 975tbr.m); 695, 850 and 810 ( th ree w bands ; 760(m); 735(w); 695(w); 670( w) ; 600( ; 565( vw) ; 540( vw) ; 42O( vw)

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0x0-CATION COMPLEXES. X I 1 1

TABLE 3 (Contd.)

155

Pomplex/Ligand Band (cm-’)

3640-3000( br ) ; 2400( vw) ; 2300(vw) ; 167&1580(br, not well resolved with severa l peaks); 1550(m); 14&O(br,rn)- 1350( br,w) ; 1305( vw) ; 1230( s) ; 11 5 O t s) ; 1080(w ; 1025(vw); 945(br,w) ; 875(rn) ; BlO(vw]; 760(s); 650(v).

3600-3000 (br, band not well resolved); 2915 (br,,.r); 2380-2290 ( b r , m with two peaks a t 2350, 2330); 1700-1500(m, with two Deaks a t 1600. 1560): 1480-1410(br. m peaks 2 t 1455 i 4 3 5 ) ; - i x p ~ ( b r , w); ‘

128O(w); 1115 sj; 958(vw); 930(m); w ) ; 840(wj; 765(m); 632(w); 610(w);

364O-3000( br) ; 2900( br,w) ; 2380-2280( S , s p l i t i n to two peaks -t 2345 and 2330); 1700-1500 ( b r m w i t h t h r e e peaks a t 1600 and 15551; 156C(sh); 1470-1410(br, m with two peaks a t 7430, 1460); 3410- 1210(br, w with --Vera1 peaks); 1000(br, m w i t h a sh a t 1170). 935(s

420 (vw); 375(m).

670 w ; 840(m); 760(sj; 635(s{j 610{~{ ; 570, 530, 470,

s = strong; IP = medium; w = weak; vw = very weak;

b r = broad; sh = shoulder; vs = very strong.

due t o the presence of water molecule( s) and o r hydroxyl groups

[complexes

group(s) [complexes (2). (z) , (11, (5) and (5) -7 25926.

s t r e t c h i n the complexes (2) t o (2) observed as medium-weak broadlor

sharp peak i n the region 3300-3100 cm

complexes is observed around 1645-1630 crn” (which i s 1025 cm” lower

than t h a t observed i n t h e free l igand) and lend support for the

coordination of h i n e nitrogen 25-28.

group ( 6 as(COO) was observed a t 1720-1680 ern-', suggesting a mononu-

c l e r r formulation of t he complexes. The phenolic (c-o) generally

appears around 1500 cm” in the free Schiff base and 1540 cm” when

attached t o a s ing le metal ion ( n o n b r i d ~ F n g ) ~ ’ ~ ’ ~ & ~ ~ .

($), (2),7 and a l s o due t o the presence of f r e e COOH

The N-H

The (c=N) in the -1 25,26 ,

A band due t o the f r e e carboxyl

On the o ther

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156 DEY ET A L .

OH

CHz-N OH @

‘ 0

O H 0

‘ 0’ H2C,

CH2- N

H OH

F I G . 5

hand, t h e br idging phenol ic 6 (c-o) a?pears a t 1560 cm”. Hence, t h e

h i g h e r energy s h i f t of t h e band h a s been used f o r a d iagnos is of t h e

f o r n a t i o n of phenol ic oxygen br idge. On t h e b a s i s of t h i s we can

safely say t h a t present oxo-cation complexes a l p mononuclear in

n a t u r e with a free COOH group. The i n f r a r e d s p e c t r a of t h e complexes

(2) and (z) , show an in tense absorp t ion i n t h e 888-923 cm” region

a t t r i b u t a b l e t o t h e $ as ( U 0 2 ) mode31s32. The 4 ,(UO2) v i b r a t i o n s in

t h e s e complexes a r e expected t o be weaker in i n t e n s i t y ; t h e i r presence

could not be e s t a b l i s h e d unequivocally s i n c e t h e l i g a n a a b s a h h t h i s

region.

1380 an”, where t h e f r e e NO; ion i s known t o absorb.

be conclEded t h a t t h e two NO;

this complex (1) shows absorpt ion peak a t about 1470 cm” and 1240 an-’,

which a r e ass ignable t o t h e 4, ( N O s t r e t c h i n g ) and J b ( N O 2 assymetr ic

s t r e t c h i n g ) v i b r a t i o n , respectively3F36; it i s presumed t h a t in t h e s e

complexes the n i t r a t e ions a r e coordinated with t h e metal i on a s

un identa te l igands. It is t h u s p l e u s i b l e t h a t t h e dioxouranium(V1) ion

i n the coEplex (1) may a t t a i n e i g h t c o o r d i n a t i ~ n ~ ~ (Fig. 5).

a t e n t a t i v e suggestion.

The complex (A) does not show any absorpt ion band n e a r about

It may, thereforw,

i o n s a r e bonded t o t h e UO;’ ion. Since

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1.

2.

3.

4.

5.

6.

7.

8.

0.

10.

11.

12.

0x0-CATIOK COMPLEXES. XI11 157

The in’rared. bands f o r \i(v=o) of t h e complexes (2) t o ($) ape

observed i n t h e range 95&?60 an”, which i n a l l p r o b a b i l i t y support

monomeric V=O u n i t in these c h e l s t e ~ ~ ~ . 1 lower t h a n t h e value observed (996 cm- ) for d(,=,) in VO(aczcJ2. The

s l i g h t decrezse in V=O s t r e t c h e s of t h e present vanadyl c h e l a t e s nzy

be due t o t h e s t ronger l igand f i e l d s of t h e S h i f f base H,+fsedien.

The V=O s t r e t c h i n g frequency in t h e 0x0-vanadium(Y) comglex (21, observed a t 935 an”, which i s s l i g h t l y lower t h a n t h o s e observed

f o r u;aloeous 0x0-vanadium( N) complexes. 9 u t t h e d i f f e r e n c e in

oxida t ion s t a t e s of t h e meta: i n t h e s e two types of compound prevents

any meaningful i n t e r p r e t a t ion.

ACKNOWLEDGEMENT

These values ape s l i g h t l y

We thank t h e C S I , New Delhi 2nd t h e CSIR, Kew Delhi f o r f i n a n c i a l

a s s i s t a n c e . We a r e a l s o g r a t e f u l t o t h e Univers i ty of Kalyani f o r

research grant. Analy t ica l s e r v i c e from RSIC, C D R I , Lucknor i s a l s o

acknowled,oed, ! L K . N. is thankfu l t o CSIR f o r a junior resesrch fel lowship.

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Received: 4 February 1991 Accepted: 1 August 1991

R e f e r e e I : K . Edgar R e f e r e e 11: A . Pidcock

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