NMR and electron spectroscopic studies of La (III), Lu (III), Nd (III), Ho (III) complexes with glutamic acid

INORG. NUCL. CHEM. LETTERS VoI.]7, pp.57-61. Pergamon Press Ltd. 1981. Printed in Great Britain.

0020-1650/8|/020057-05502.00/0

NMR AND ELECTRON SPECTROSCOPIC Lu(III),

Nd(III),

Ho~III)

J. Legendziewicz,

Institute

of

Joliet-Curie

(Received 29 September

The

coordination

different NMR a n d

electron

ions

Chemistry,

University

of

1~,

Wroc£aw,

Poland

of in

absorption

Budapest. from

meter

at

oxides

50-383

glutamio

aqueous

amino The

ratio

acid

were acid

concentration

to

in

out

spectra

equal

integration

the

recorded

in

their

which

£-f

H.

of

the

bands

environment.

obey

the

selection

used

He t o

The

the

by means

an

Asp

l&nthanide

However,

as

rules

of

it

from

Nd(IlI) in

rof.

internal

N-512

O. 1 t o

of

(or

pH-meter.

0.2

were

Glu)

1204

obtained

[ ~ ) MHZ s p e c t r o -

In

The the

pH

h~4R s t u -

M. and

strengths Odra

Reanal

standard.

the

14 s p e c t r o p h o t o m e t e r

an

and

obtained

on a JEOL JNM-PS-100

oscillator

usin~

as

given

as

from

on a Cary

0.05

in

was

the

to

transitions

towards

established

He ( I I I } a n d

on a Mera.EImat

Results The

used

recorded

varied of

were

description

D20 wore

concentration

were

was

groups

tal

Lu~III),

Dioman

oarTied

absorption

carboxyl

solutions

acid

La(III),

(FT mode).

solutions

graphic

of

accordi~

25 ~z

Wroolaw,

spectra.

L-glutamic

1~C NMR s p e c t r a

measurements dies

and

Perohlorates

metal The

acid

H. K o z l o w s k i ,

owska

Ex~rtmen L-aspartic

ACID

1980; received in revised form 24 November ]980)

ability

lanthanide

COMPLEXES WITH G L U T ~ I C

E. Huskowska,

B. Je~owska-Trzebiat

S T U D I E S OF L a ( I I I ) ,

were

Nd:Glu=l: at

1 molar

a metal

calculated

ion with

computer.

Discussion ions

was ~J

57

~

are

slightly

reported 2

(~L

sensitive

earlier(2) ~

2,

~S

,

to the

= O) a r e

char~es transitions unusually

58

NMR

sensitive

to s u c h c h a n g e s .

covalent~

dynamic

when

And Electron Spectroscopic Studies

No m a t t e r w h i c h m e c h a n i s m

coupling(l-~))would be a s s u m e d

the c o o r d i n a t i o n

of a l a n t h a n i d e

a coordinated water molecule takes place~ m a r k e d

by means

oscillator

those t r a n s i t i o n s ,

ion to a l i g a n d or the r e p l a c e m e n t

in the a q u o - i o n b y a n o t h e r

F o r that r e a s o n

tran-

c o u l d be

transitions.

s p e c t r a w e r e r e c o r d e d i n the 3 1 9 . 5

ion a n d in the 289 -

of

sclvatin~ molecule

the c o m p l e x a t i o n p r o c e s s

of the ohar~ges of h y p e r s e n s i t i v e

The absorption the Nd(III)

relevant for

c h a n ~ e s in the i n t e n s i t y of the a b o v e m e n t i o n e d f-f

s i t i o n s are o b s e r v e d . followed

(forced e l e c t r i c dipole,

- 909 nm r e g i o n f o r

1250 nm r e g i o n f o r the H o ( I I I ) ion. T h e

strengths were calculated from

the f o r m u l a

:

f

P

4.31 Io'9~ ~&~

=

v4

where

~ i is a m o l a r a b s o r b a n c e T h e pH d e p e n d e n c e

transitio~ as f o r

5I 8

,

of the o s c i l l a t o r

5G6,

the N d (III)ion

are g i v e n i n T a b l e s

c o e f f i c i e n t and

7F I

s t r e n g t h s f o r the He (III)

P

~I9/2

is

to these f o u n d

116 (pH = 2.5~)

complex

in the Nd(III)

and

Pexp 108

pH

ion

- P

with glutamic acid

aquo-lon

)

: G l u s o l u t i o n s a r e vet T

f o r A s p c o n t a i n i n ~ s o l u t i o n s a n d 91

f o r Giu c o n t a i n i n g s o l u t i o n s °

T~BLE 1 O s c i l l a t o r S t r e n g t h of 5I 8 --~ 5G6, 7F 1 T r a n s i t i o n f o r H o ( I I I ) S o l u t i o n s a t V a r i o u s pH pH

-1

: A s p s y s t e m s t u d i e d earlier(8)i.e. A P

186(pH = 4.241

(pH = 2.78) and 209 (pH -- 4.84)

cm

2G7/2

i 4G5/2,

T h e i n t e n s i t y o h a n ~ e s f o u n d f o r the N d (III) close

a wave number

w i t h a s p a r t i c a c i d and g l u t a m i c a c i d as w e l l

transition

1,2,3 { n P =

~

Pexp 108

pH

: Asp

Pexp" 108

aquo

612

2.93

7~6

5.2

896

2.k8

703

4.47

891

5.3

885

2.75

7~2

~.86

884

5.6

936

NMR And Electron Spectroscopic Studies

TABLE Oscillator Solutions

Strength

for Ho(III)

: Glu

Pox~ 108

pH

Pexp

pH

aquo

572

2.56

635

4.45

919

1.62

606

2.8

688

4.95

899

2.28

633

3,27

725

5,8

967

TABLE Oscillator

Strength

Glu Solutions

pH

3

of ~ I 9 / 2 --*

at V a r i o u s

Pex/~ 108

4G5/2

2G7/2,

Transition

pH

Pexl:; 108

pa

Pexp"

2.78

1052

4.56

1243

1,97

1002

3.16

1103

4.8h

1261

2.52

1027

4.38

1241

5.03

1258

libria

are

similar It

the

~

P value

the

same,

lue

was the

is

first

these

observed

two t i m e s

for

absorption

higher.

different

that

for

second That

might

group

or

spectral

= 5.3)

coordination

presented

above

suggests

in a s i m i l a r way, NMR data f o r

which

the

of

the

by its

different

behaviour ~P to

i.e.

coordination

to

containir~

COO- g r o u p group the

equi-

Nd(III),

was a l m o s t

the

~

stronger

coordination

is o b s e r v e d f o r

P va-

bonding

mode

I8).

the He iIII) : A s p

c a u s e d by a c o o r d / n a t i o n

of the

133 a n d

of the

~P

the c o o r d i n a t i o n

only s l i g h t l y groups

they are s i m i l a r

w i t h A s p a n d Olu. The

that GIu c o o r d i n a t e s is not

~

carborFlio

of the G l u c a r b o x y l

complexes

the La(III)

systems

be due either

increases

f o r pH = 2.8 and 221 for pH = 4.95 the case of the Nd III

that

the

coordinated

g r o u p ( pH < 3) is equal

second c a r b o x y l g r o u p ( p H a correspondin~

all

coox~Ltnation

In the HoIIIII : A s p s o l u t i o n

carboxyl

spectra

108

systems,

for

the

oarboxylio

Slightly system.

in

the

characteristic

whereas

second

from

:

pH

961

appears

1o 8

f o r Nd{Ill)

aquo

It

of

7F 1 T r a n s i t i o n

pH

Pexp 108

pH

2

of 5I 8 ---# 5G6,

at V a r i o u s

59

to

140. For

to H o ( I I I 1 ~ P

= 116

to those f o u n d in spectroscopic

to light a n d h e a v y

data

lanthanldes

the case f o r Asp. a n d Lu(III)

c o m p l e x e s w i t h G l u are p r e s e n t e d

60

NMR And Electron Spectroscopic Studies

in Tabte

/4.

dination

to Glu at

1.1 a n d All

shift

pH 2 . 5 6

1 . 0 ppm d o w n £ i e l d

other

tion

1~C c h e m i c a l

at

carbons this

pH r e g i o n

to

the

ion,

and Lu(IlI)

. The do~ield

L,(III)

of

ion

metal

ion

to

and a water

this

are

These

metal

and

the

may d e r i v e

Ln(III)

s y ,

t

e -

Shifts

pH

mode i s

are

~ CO0- i n

the

coordina-

bound in

similar

for

tbLs

La(IlI)

presence

coordination

bond formation

of

the

o£ t h e

between

~ C00H

/4

of GIu

Qcoo~"

Ocoo~

p.p.m Glu c = 0.1 M

ton

~ COO" i s

from partial

they

~ COO- c a r b o n s .

to metal

that

of

and

coor-

aquo-ion.

TABL~ 13C c h e m i c a l

1.0 for

ooordXnatton shift

Lu(III)ion

similar

Insensitive

or from hydrogen

the

are

and

s~ggest

chemical

~ COO- g r o u p of

rather

results

pH r e g i o n

molecule

by La(III)and

~ COO- a n d 0 . 9

C ~

pH r e g i o n .

caused

( ~ COO- d e p r o t o n a t e d ) for

expect

changes

p.p.m

Ocp

~c~

,~c~-

p.p.m

p.p.m

p.p.m

2.59

110.1

106.5

-13.1

--36.8

-/41.-3

= 1:1 0.2M

2.57

111.0

107.6

-1-3.0

--36./4

-741.3

L u : G l u = 1:1 o = O.2H

2.56

111.1

107.5

-1-3.0

-36./4

-/41.3

Glu

/4.8/4

113.6

107.8

-12.1

-3/4.0

-39.9

/4.79

117.2

108.5

-12.3

-33.6

-/40.5

/4.81

117.8

108./4

-12.3

-.3/4.0

-/40.5

La:Glu o

=

o = 0.2 M

La:Olu c

= 1:1 = 0.2g

L u - Gku = 1:1 c = 0.2H At a higher field This

shift

indicates

The it

~ is

(Table of 0.6 that in

of

pH r a n g e

~ COO- c a r b o n

of

that

~ C00- group

also

ligan4

pH m n ~ e

shifted

pH r e g i o n

the La(III)

~ COO- r e - s i n s the

this

up£ield

/4~. A t t h e ppm f o r

/4.8 m e t a l

the

CO0- s h X £ t a t

slightly

above

bound

molecule

is

as above

tons

3.6(La

is

almost to

/4.8 a l s o

the

metal

the

CA

ion

not

the

same a s

and

that

to

eqtml

the

for

both

solutions

that

the

metal at

This

charge

o f pH ~ 2 . 6 .

tons. ions

and

pH 2 . 5 6

an up~ield

solution.

down-

(Lu ( I T I I ) .

lanthanide

undergoes

containing

to

a oonstdex~able

~ I I I ) ) a n d /4.2 ppm

coordinates

compared

and LulIII )

caused

sh4ft

stq~geste distribution

NMR And Electron Spectroscopic Studies

The c o n s i d e r a b l e difference in

i~ COO"

Glu a n d

in Asp strongly s ~ g e s t s

of those groups w i t h lanthanide strengths

in the chemical

shifts of b o u n d

a different

~ COO-

c o o r d i n a t i o n mode

ions. This m a y result f r o m t h e different

of the chemical bends or f r o m the different

lexes e.g. A s p m a y f a v o u r

6

g e o m e t r y of t h e comp-

the f o n a a t i o n of the chelate complex more

than

Glu since in the latter case, a t h e r m o d y n a m i c a l l y unstable eight m e m b e r e d rin~ has to be

formed.

In the latter case the f o r m a t i o n dimerio or polyme-

ric species is more likely. ctra were n o t able 13C NMR spectra

As was m e n t i o n e d

to distinguish,

between

of the lanthanide

detect chan~es in the a m i n o a c l d molecule

the a b s o r p t i o n

spe-

those differences found in the

. E l e c t r o n s p e c t r o s c o p y m a y allow

in the closest environment

lanthanide

previously

to f i n d the d i f f e r e n c e s

ion while

the N M R parameters

caused by its i n t e r a c t i o n w i t h

ion (8-10).

References

I.

J.LEGENDZIEWICZ, Phys.Aoad.Sci.,

K.BUKIETY~SKA Hungary,

~5,

2. C . K . J ~ R G E N S E N and B.R.JUDD, 3. B.R.JUDU,

J.Chem. Phys., 4~4,

and B.JETOWSKA-THZEBIATOWSKA,Aota

187

1971

Mol. Phys., --8, 281 839

1964

1966 B.

4. D . E . H E N R I E and G.R.CHOPPIN, J.Chem. Phys., 49, 477 5. K . B U K I E T Y ~ S K A

and G.R.CHOPPIN,

6. S . F . H A S O N , R . D . P E A C O C K

J.Chem. Phys.,

and B.STEWARD

7- R.D.PEACOCK, S t r u o . B o n d l n g ,

22,

83

1968

52, 2875

Mol. Phys., 30,

1829

14, 4o9-141

and E.BURZALA,

J.Am.Chem.Soc°,

a n d EoHUSKOWSKA,

Inorg.Nucl°Chem.Lett. ,

1978

10. A.D.SHERRY a n d E.PASCUAL,

1975

1975

6 . J.LEGENDZIE~/ICZ, H.KOZLOWSKI, B.JE~OWSKA-TRZEBIATOWSKA Inorg.Nucl.Chem.Lett. , 15, 349-353 1979 9. J . L E G E N D Z I E W I C Z , H . K O Z L O W S K I

1970

99,

18

1977