Antiferromagnetic binuclear halogen-bridged dithiocarbamate complexes of copper(II)

1N0R6. NucL. CHEM. LE77ER5. v01. 12, pp. 501-503, 1976. Per9am0n Pre55. Pr1nted 1n 6reat 8r1ta1n.

AN71FERR0MA6NE71C

81NUCLEAR

HAL06EN-8R1D6ED

C0MPLEXE50F R.H.

Furneaux,

and Ekk 51nn,

D17H10CAR8AMA7E

C0PPER(11)

Chem15try

Department,

V1ct0r1a

0f We111n9t0n,

We111n9t0n,

New 2ea1and

Department V1r91n1a,

0f Chem15try,

Un1ver51ty

Un1ver51ty

Char10tte5v111e,

0f

VA 22901

~e1v~20Fe6~a~197~ React10n50f c0pper(11)

ha11de5,

pr0duce51:1 decrea5e

CuX2,

adduct5

n1tr09en

c0nf1rm,

1n a v a r 1 e t y

t00ccur

temperature

temperature

a 61nuc1ear

5u5cept16111ty

d1th10car6amate5,

max1mum

ju5t w 1 t h 1 n

d0wn

he11um

t0114u1d

5u5cept16111ty

wh1ch

(F19.

61nuc1ear

c0mp1ex,

1) c 0 r r e 5 p 0 n d 1 n 9

c0pper(11)

Nd = 6 x 10

c0mp1ex

-5

c95emU,

N 2) t e m p e r a t u r e

ran9e,

unam619u0u5 ma9net1c

data

are c h a r a c t e r 1 5 t 1 c

0f a

t0 E4.

15 e 5 t 1 m a t e d

fr0m the

the 0ther

5ym6015

the1r

have

7he

1mpur1ty

up 1n the m 1 c r 0 a n a 1 y 5 e 5 , temperature

u5ua1

pr0pert1e50f

mean1n95. 5eparat10n

repre5ented

0n1y

and

at the

11m1t

0ther

7h15 y1e1d5 -2J,

1t5 c 0 n t r 1 6 u t 1 0 n

w1th

than

a va1ue

9 = 2.06, t05h0w 10w

t0 the m a 9 n e t -

temperature5.

{Cu(dtc)C1} 2 c 0 m p 1 e x e 5

501

0f the data;

6y p 15 t 0 0 5 m a 1 1

10we5t

(1)

0f p a r a m a 9 n e t 1 C

0r any m e a 5 u r e m e n t 5 0 t h e r

5u5cept16111t1e5,

15m 15 n 0 n - n e 9 1 1 9 1 6 1 e

+ Ne + 10.92P77

10w t e m p e r a t u r e

0f 98 cm -1 f0r the 5 1 n 9 1 e t - t r 1 p 1 e t p = 0.016.

(1) f0r a "5p1n-

(3) :

and p, the p r 0 p 0 r t 1 0 n

1mpur1ty,

ma9net1c

appeared

{Cu(822dtc)C1} 2, ha5 m a 9 n e t 1 c

×M - N923k782(1+~e-2J/k7)-1(1-P)

where

6ut d1d n0t

7he m a 9 n e t 1 c

We n0w rep0rt

temperature

d0wn

5tructure.

7he N , N - d 1 6 e n 2 y 1

0n1y"

(114.

and d1d n0t perm1t

0f the re5u1t5.

61nuc1ear

5u99e5ted,

(3) f0r 5uch d1mer5

the a v a 1 1 a 6 1 e

1nterpretat10n

m0ment5

Mea5urement5

{Cu(dtc)X] 2.

expected

n0t w e 1 1 - d e f 1 n e d

ma9net1c

(1,2).

(1,2)

5tructure

Cu(dtc)2 , w1th

0f a n h y d r 0 u 5 5 0 1 v e n t 5

Cu(dtc) 2.CuX 2 w h 0 5 e

w1th decrea51n9

t0114u1d

6ut wa5

c0pper(11)

are

7he 51m11ar,

502

~10car6am~e

1

C0mp~x~

•

1

~ C0p~r

•

(11)

1

•

2

7 103~<~M

100

200 7¢K) >

300

F16. 1 Exper1menta1 and ea1cu1ated ma9net1c 5u5cept16111ty

(XM) f0r

~(~tc)c1}~ 7A8LE 1 R 1n {Cu(R2dtc)C1} 2

J(cm -1)

(6en2y1) 2 (n-pr0py1) 2 (n-6uty1) 2

a5 1 n d 1 c a t e d 51m11ar

7he c r y 5 t a 1 X-ray

data

5tructure5 6etween

(F19.

that

the

0pp05e 11nk5.

(7a61e

m01ecu1e5

065ervat10n

(6,7)

(4,5)

a very

and p r e 1 1 m 1 n a r y

the 6 1 n u c 1 e a r weak

(d1mer1c)

0ut-0f-p1ane

1nteract10n5

E4.

(1)

c0mpared

15 1n k e e p 1 n 9

w1th

1nterm01ecu1ar

a5 d0 w e a k

6r1d9e5

tetramer1c

w1th

are u n 1 m p 0 r t a n t 7h15

that 0 u t - 0 f - p 1 a n e

1nteract10n5,

119and

11nked

0f the m a 9 n e t 1 5 m

1nteract10n5.

ma9net1c

-70 -68 -50

1mp1y1n9

t0 f0rm a w e a k 1 y

c0nf0rm1ty

1nter-d1mer

1),

0f 0ne c 0 m p 1 e x

1) and 1 n d 1 c a t e

1ntra-d1mer

5tr0n9

(n-penty1) 2 (n-hexy1) 2 (6en2y1, n~pr0py1)

(5) c 0 n f 1 r m

H0wever,

J(cm -1)

ca5e.

5tructure

the d 1 m e r 1 c

1mp11e5

9enera1

1n each

0n a n 0 t h e r

5tructure.

w1th

-49 -55 -65

6y the -2J v a 1 u e 5

5tructure

R 1n {Cu(R2dtc)C1} 2

the

11nk5

1nterm01ecu1ar

D1th10car6amate C0mp1exe50f C0pper (11) 0x1dat10n 0f r e a c t 1 0 n

and r e d u c t 1 0 n

e5pec1a11y

Cu(5CN) 2 are u5ed 7hu5

0n1y

w1th

n0n-ch10r1de

1n p1ace

tw0 c 0 m p 1 e x e 5

F0ner

techn14ue5

read11y

0f CuC12

1n 900d

Cu(C104)2

type have

{Cu(Et2dtc)8r~and

mea5urement5

1n th15

t0 react w 1 t h

were

carr1ed

and 5QU1D m a 9 n e t 0 m e t e r 5 ,

6e1n9

0ccur

Cu8r 2, Cu(N03)2,

0f the a60ve

119and5,

7he m a 9 n e t 1 c Faraday,

when

(2,8)

503 type

and

Cu(dtc) 2.

50 far 6een

f0rmed

{Cu(822dtc)8r} 2 • 0ut u51n9

the data

60uy,

fr0m the var10u5

a9reement.

Reference5 1.

Paper

2.

R.H.

pre5ented

1n Me160urne,

New 3.

A.R.

7he515,

2ea1and,

c1ted 4.

Au5tra11a,

FURNEAUX,

E. 51NN,

(6y E.5.)

at the 39th A.N.2.A.A.5. January

V1ct0r1a

C0n9re55

1967. Un1ver51ty

0f We111n9t0n,

1972.

C00rd.

Chem.

Rev.,

5, 313

(1970)

and r e f e r e n c e 5

there1n. HENDR1CK50N,

R.L.

C0mmun.,

843

5.

E. 51NN,

unpu6115hed

6.

E. 51NN,

1n0r9.

7.

H. Y0K01

and

8.

P.7.

MAR71N

and D. 7AYL0R,

J.C.5.

Chem.

(1975). data.

Chem.,

1n pre55.

M. CH1K1,4A,

J. Amer.

Chem.

50c.,

and J.J.

57E66ERDA,

97,

3975

(1975) . 8EUR5KEN5,

7, 810 377

(1968);

(1971);

(1972) ; R.M. 7ENNAN7,

J.A. H.C.

E.A.

CRA5

8R1NKH0FF,

PA5EK

60LD1N6,

Au5tra11an

Rec.

and D.K. C.M.

HARR15,

J. Chem.,

7rav.

57RAU8,

25,

K.J. 2567

1n0r9.

Ch1m.

Chem.,

Pay5-8a5,

1n0r9.

Chem.,

JE550P

and W.C.

(1972).

11,

90~ 259