Some new sulphinate complexes of cadmium

INORG.

NUCL. CHEM. LETTERS Vol. 11, pp.

SOME NEW

SULPHINATE

Martin University

J. M a y s

Chemical

381-385, 1975. Pergamon Press. Printed in Great

COMPLEXES

OF CADMIUM

and Pauline

Laboratory,

Britain.

A. V e r g n a n o

Lensfield

Road,

Cambridge.

~eceived 16 December 1974)

been

Although

a large

prepared

in r e c e n t

little

attention.

or p - t o l y l ) , complex

and

ligands these

Only two

Cd(OzSR)2

of s u l p h i n a t e

number

complexes employed.

N-donor

ligands

the

be

dihydrate, (designated

have

upon

not

received (R=phenyl

a and ~)

anhydrous

the n a t u r e

of the

report

containing the

that

a series

nitrogen

been

donor

stoichiometry

of the n i t r o g e n

sulphinate

previously

have

have

(H20)2Cd(O2SR)2

and that

IIB metal

complexes

of c a d m i u m

We n o w

of c a d m i u m

synthesised

Group

sulphinate

those

are k n o w n ( 2 , 3 ) .

depends

ligand

years(1),

forms

complexes

can a l s o

of m e t a l

complexes

of

donor containing

described.

Experimental The

complexes

L4Cd(02SPh)2

(L2=en)

stoichiometric o-phen

(0.90

suspension

ethanol and

of

were

quantity

a-Cd(O2SPh)2

(20 ml).

A clear

(L2=bipy

prepared

of the

g, 0 . 5 m m o l e )

the p r o d u c t ,

powder

L2Cd(02SPh)2

was

from

ligand. added

(0.197

g,

solution

on e v a p o r a t i o n

of the

solvent.

381

o-phen)

and

a-Cd(O2SPh)2

using

In a t y p i c a l

experiment

to a v i g o r o u s l y

0.5

was

(o-phen)Cd(O2SPh)2)

or

mmole)

obtained

was

in

stirred refluxing

almost

obtained

a

immediately

as a w h i t e

It w a s w a s h e d

with

dry

382

Sulphinate Complexes of Cadmium

acetone

and dried

prepared and

under

in a s i m i l a r

a 3:1

excess

obtained

washed

acetone

with

ligand.

and 2 moles

precipitate

with and

new

infrared o-phen

and be

and

the

other

and give

present, of

complexes

diaquo

hand,

gives

from

The

complexes

few weeks and

unless

the p y r i d i n e

per

t h e y are

The

in a q u e o u s

of

these

is m o r e be

basic

will

prepared The white

filtered

systems,

is

The

stable.

synthesised

Table

seen

off,

No

thus

together

that

py,

en,

oil

the dark.

complexes of

over

the

ratio

by water

two

of

are of a

complexes

to g i v e compound,

It

is u n a f f e c t e d

by light

from

the d i h y d r a t e

using

of light

the o~

or water

water

however,

liberating

4

could

a period

These

does,

the

respectively

bis-ethylenediamine

complex

that

on

(o-phen)Cd~2 S Ph)2

decomposed

in the p r e s e n c e

are to

ligand,

other

bipy

atoms

analogous

irrespective

and

I

donor

containing

to a y e l l o w in

be

nitrogen

atom.

tris-ethylenediamine

solution

was

in

N-donor

of c o m p l e x

are also

hand,

solvent.

two

stored

the

in f a c t

which

and decompose

(H20)2Cd(02SPh)2.

and may

It

cadmium

dihydrate other

was

reported

data.

(bipy)Cd(02SPh)2

~omplex

(H20)2Cd(02SPh)2

in e t h a n o l .

reagents

are

more

types

the a b o v e

employed.

sensitive

The

two

atoms

the

was

Discussion

stoichiometry

reactants

light

in

complex°

the d i h y d r a t e

(pY)2Cd(02SPh)2

prepared

complexes

6 nitrogen

isolated

and

analytical

the

(en)~Cd(02SPh)2

dried.

Results The

complex

of p y r i d i n e

on mi~ing and

The

using

manner

of the

from ~-Cd(02SPh)2

vacuum°

Vol. 11, No. 6

as

the

dissociate

ethlenediamine

Vol. 11, No. 6

Sulphinate Complexes of Cadmium

383

O'x

®

~

o

O0

~

~

~

Oh

~

"{") 0

~

'~0

~

T-•

--

•

~"

'r'-

C~

'~" °

o

-r,I ID @

~

oO

~

II

-;-I ,-I 0 ,m

0",

m ['~ Oh

~r% Lr% O'x

o o 0 ,~-

!

0

O.,I ~ v

0

I

0

~ .-... ~0 ~--.~

0

0

0

0

0

II oz o

~

0 ~

0

0 ~

~

0

0

0

r.D

~

•

0

0

.~ '0

~

E

o 0 0

II ;.Q

0

~

r-I

r~

o

..Q

384

Sulphinate Complexes of Cadmium

The spectra

absence

of the n e w

sulphinate bonded 1100 are

complexes

similar

bidentate possible

The

case

from

Although

there

it is n o t e w o r t h y

the~

tentative -~ (S02)

cadmium

bands

whether

two m e t a l

the

cadmium

are no

with

of the

spectra

by

the

obscure

of the

a frequency than

cm -1

in

difference

that

expected

ligands. in

For

that

are

the

cadmium

(en)2Cd(02SR)2

in the O ( S 0 2 ) suggests ligand.

and

region

that The

the

to

spectrum

contains

cm

due

-I

to

(en)2Cd(02SPh)2 a n d 967 and J

as

as o p p o s e d these

is m o r e

close

cm -I

bands

occur

in w h i c h

of the

than

be

tris

other

to

which

s

our

is

to 0 , 0 ' at

0However,

six-

similarity

of the

possibly

the

in w h i c h

to be p r e s e n t ( 6 ) .

these

en m a y

are

ligands(5).

a complex

atom

the

complexes

vibrations

comparison,

thought

is

octahedrally

(NH3)2CdC12

between~

(bipy)2Fe(02SR)2,

ligands

are

1100-900

for O-

are

ethylenediamine

that

the r e g i o n

not

Whichever

analyses

chloride

fact

contain

ligands

related

complex

bridging

the

atoms

closely

the

transition

complexes

atoms.

crystallographic that

complexes

It is h o w e v e r ,

1015

unlikely

monodentate

ligands.

1250-

of r e l a t e d

the

at 1 0 3 0 s h ,

sulphinate

complexes

that

S-

a n d the s m a l l f r e q u e n c y

of b a n d s

and 918

spectrum

and

assignment

sulphinate

coordinate

complex

spectra

since

and o-phen

For

gives

seems

bipy

infrared

in the r a n g e

to o c c u r .

bonded

it

to k s

expected

smaller

bonded

due

t h a n S- b o n d e d

are

rather

1054

X-ray

is c o m p l i c a t e d

(S02)

rather

suggests

s

that

available,

partially

contain

they bridge

for which

en l i g a n d

they

the

of c a d m i u m

complexes

that

(bipy)Fe(SO2R)2(4),

and ~

likely

Interpretation

indicates

sulphinate

or w h e t h e r

six-coordinate

in the

of the py,

as

as

to d e t e r m i n e

coordinated.

cm -I

of the d i a q u o

0,0'-bonded

it s e e m s

1100

a frequency

such

between ~

above

are O-

spectra

to t h o s e

chelating, the

which

show

derivatives

difference

complexes

ligands

cm-1(1).

metal

ofq/(S02)-%-" b a n d s

Vol. 11, No. 6

of the

0,0'-bonded

acting

as a

en c o m p l e x

is

Vol. 11, No. 6

similar as

Sulphinate Complexes of Cadmium

to that

of r e l a t e d

[(bipy)sFe][02SR]2

the ionic

formulation

We have sulphinate

recently

complexes

shown

probably

because

sulphur

a t o m less

that

a number

complexes,

involves

a t o m as the first

perhaps

such

that it too s h o u l d be g i v e n

of 0 , 0 L b o n d e d

of the G r o u p IB m e t a l s

oxidation

complexes

derivatives

[(en)sCd][02SPh]2.

to s u l p h o n a t e

sulphinate

transition metal

and s u g g e s t s

oxidation

sulphur

385

reported

the m o r e

and that

nucleophilic

step(7).

susceptible

None

charged

the m e c h a n i s m

attack

air-

of this

of o x y g e n

at the

of the G r o u p I I B

here u n d e r g o

highly

readily undergo

this

cadmium

to n u c l e o p h i l i e

oxidation, atom r e n d e r s

the

attack.

REFERENCES I

.

G. V I T Z H O H 315

2.

and Eo LINDNER,

Ar.gew.

Chem.

Int.

Edit.,

10,

(1971).

G.B.

DEACON and P . G .

C00KSON,

Inorg.

C00KSON,

Aust.

Nucl.

Chem.

Lett.,

5,

607 (1969). 3.

G.B.

DEACON ~LUd P . G .

J.

Chem.,

26,

1893

(1973).

4.

E.

LINDNER,

211

5.

C.H.

I.P.

LORENZ a n d G. Ir~TZhq3M, Chem.

Ber.,

106,

(1973). MacGILLAVRY

and J.B.

BIJVOET,

Z. Krist,

A94,

231

1032

(1972).

(1936). 6.

E. L I N D N E R

7.

J. B A I L E Y

(1974).

and I.P. and M.J.

LORENZ, MATS,

Chem.

Bet.,

J. O r g a n o m e t a l .

105,

Chem.,

6__23, C24