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Deprotonated N-sulphinylphenylhydrazine complexes of Cu(II) and Hg(II)
INORG.
NUCL.
CHEM.
LETTERS
Vol. 7, pp. 733-735, 1971.
Perwunon Press.
Printed
in
Great
Britain.
DEPItOTONATED N-SULPHINYLI~F2~I2qYDRAZINI~COMPLEXESOF Cu(II) AND Hg(II) W. K. Glass and J. O. McBreen Department of Chemistry, University College, Dublin 4, Ireland. (Received 17 March 1971;
The novel complexes Cu(PhNNS0)2.H20 and Hg(PhNNSO)2 have been prepared and examined.
These ccmpounds are derivatives of N-sulphinyl-
phenylhydrazine, PhI~INSO. Attempts have previously been made to coordinate the -NS0 group to a t r a n s i t i o n metal (1). was (Z) in the preparation of Hg(NSO)2.
The only success
A Biels-Alder type of
addition can take place across the NfS bond of the -NSO group; ex~nples of t h i s reported to date are the reaction of N-sulphinylaniline (PhNSO) with CsH5.Fe(CO) 2"Ot2C=O4e to form a metal vinyl complex containing a 1,2-thiazine 1-oxide cyclic system, (3), and of PhNSO with Fe2(03)gtO y i e l d Fe2(O3) 6.PhNS, (41. N-sulphinylphenylhydrazine (Ph~SO) was prepared by the method of Michaelis, (5), O.39g. (1.3 x 10-3 moles) of Ph~Nso (A) dissolved in 10 ml. ethanol was added to O.25g. (2.6 x 10-3 moles) of copper (II) acetate in 10 ml. water. were employed.
A nitrogen atmosphere and constant s t i r r i n g
A dark brown p r e c i p i t a t e , which analysed s a t i s f a c t o r i l y
for Cu(Ph~qSO)2.H20 (B), formed quickly.
Compound B was stable in a i r ,
but decomposed slowly in benzene to y i e l d copper (I) phenyl mercaptide and copper (II) oxide; i t deccmpesed v i o l e n t l y at 86°C, and was monomeric in benzene solution.
Ligand A could be recovered by protonating
compound B with dilute hydrochloric acid in alcohol solution; this was evidenced by a sh~ft in a strong band at 27,700 on an n
÷
~
*
transition) to 28 ,O90 on
-1
733
--i
.
in B (presumably
and by analysis of the recovered
734
COMPLEXES OF Cu(ll) ANF Ha(Ill)
product.
Vol. 7, No. 8
Using the Gouy method on the s o l i d s~uple, a magnetic moment
o f 2.0 B.M. was obtained.
In benzene s o l u t i o n , the magnetic moment
was determined by an N.M.R. method (5), and found t o vary between 1.2 and 1.8 B.M. presumably because o f decomposition.
The presence o f
copper ( I I ) was t h e r e f o r e i n d i c a t e d . A d-d t r a n s i t i o n a t t r i b u t a b l e t o copper ( I I ) was observed at 20,500 on-1.
The F..S.R. spectr~n o f the bulk s o l i d at 25°C c o n s i s t e d
o f a n o n - i s o t o p i c d e r i v a t i v e curve, with gl = 2.089 and g2 = 2.148. The i n f r a r e d spectrum of B contained no N-H s t r e t c h i n g or bending modes.
Bands at 12~0 on-1 and 1085 an -1 a t t r i b u t a b l e t o ~as(NSO)
and vs (NSO) in the ligand A were s h i f t e d t o 1280 and 950 on-1 respectively.
Bands a t 527 and 285 an -1 are assignable t o Cu-N
s t r e t c h i n g modes. Ethylene di~nine (en) r e a c t e d with B in dry benzene t o produce Cu(en) (PhM~SO)2. This compound was extremely unstable in a i r .
On
the basis o f the above o b s e r v a t i o n s , we conclude t h a t Compound B i s probably a pyr~nidal square-planar complex, with copper bonded t o the oxygen and n i t r o g e n atoms adjacent to the benzene r i n g s , water occupying an a x i a l p o s i t i o n . Mercury ( I I ) a c e t a t e r e a c t s in a q u a n t i t a t i v e manner under s i m i l a r r e a c t i o n conditions to form Hg(PhNNSO)2, a b r i g h t yellow compound o f s a t i s f a c t o r y analysis which decomposed e x p l o s i v e l y at 69°C.
This complex possesses an n ÷ r
bond a t 27,700 an -1.
I n f r a r e d bands assignable e s s e n t i a l l y t o ~as(NSO) and ~s (NSO) occur a t 1288 and 10(]O on -1 r e s p e c t i v e l y .
Mercury-nitrogen v i b r a t i o n s
are found at 280 and 255 an -1. Caution must be e x e r c i s e d in the r o u t i n e handling o f these ccmrpounds due t o t h e i r tendency t o detonate.
Vol. 7, No. 8
COMPLEXES OF Cu(Ii) AND HI~Ii)
References 1.
N. COLLINS and W. K. GLASS, Chron. CAlm., 211(1967).
2.
W. VERBEEK and W. S l ~ ,
Angew. Chin. internat, ed.
8_, 376(1969). 3.
P.W. ROBINSON and A. WOJCICK, Chest. Comm., 951(1970).
4.
S. OTSUI(A, T. YOSHIDA, and A. NAKAMIJRA, Inorg. Chem., 7,
1833(1968). S.
A. M I ~ I S ,
6.
H . P . FRITZ and K. E. SOIRARZHA~, J. Orgmlometal. Chem., 1_, 2OS(1963).
Bet., 2_22, 2228(1889).
7,35
NUCL.
CHEM.
LETTERS
Vol. 7, pp. 733-735, 1971.
Perwunon Press.
Printed
in
Great
Britain.
DEPItOTONATED N-SULPHINYLI~F2~I2qYDRAZINI~COMPLEXESOF Cu(II) AND Hg(II) W. K. Glass and J. O. McBreen Department of Chemistry, University College, Dublin 4, Ireland. (Received 17 March 1971;
The novel complexes Cu(PhNNS0)2.H20 and Hg(PhNNSO)2 have been prepared and examined.
These ccmpounds are derivatives of N-sulphinyl-
phenylhydrazine, PhI~INSO. Attempts have previously been made to coordinate the -NS0 group to a t r a n s i t i o n metal (1). was (Z) in the preparation of Hg(NSO)2.
The only success
A Biels-Alder type of
addition can take place across the NfS bond of the -NSO group; ex~nples of t h i s reported to date are the reaction of N-sulphinylaniline (PhNSO) with CsH5.Fe(CO) 2"Ot2C=O4e to form a metal vinyl complex containing a 1,2-thiazine 1-oxide cyclic system, (3), and of PhNSO with Fe2(03)gtO y i e l d Fe2(O3) 6.PhNS, (41. N-sulphinylphenylhydrazine (Ph~SO) was prepared by the method of Michaelis, (5), O.39g. (1.3 x 10-3 moles) of Ph~Nso (A) dissolved in 10 ml. ethanol was added to O.25g. (2.6 x 10-3 moles) of copper (II) acetate in 10 ml. water. were employed.
A nitrogen atmosphere and constant s t i r r i n g
A dark brown p r e c i p i t a t e , which analysed s a t i s f a c t o r i l y
for Cu(Ph~qSO)2.H20 (B), formed quickly.
Compound B was stable in a i r ,
but decomposed slowly in benzene to y i e l d copper (I) phenyl mercaptide and copper (II) oxide; i t deccmpesed v i o l e n t l y at 86°C, and was monomeric in benzene solution.
Ligand A could be recovered by protonating
compound B with dilute hydrochloric acid in alcohol solution; this was evidenced by a sh~ft in a strong band at 27,700 on an n
÷
~
*
transition) to 28 ,O90 on
-1
733
--i
.
in B (presumably
and by analysis of the recovered
734
COMPLEXES OF Cu(ll) ANF Ha(Ill)
product.
Vol. 7, No. 8
Using the Gouy method on the s o l i d s~uple, a magnetic moment
o f 2.0 B.M. was obtained.
In benzene s o l u t i o n , the magnetic moment
was determined by an N.M.R. method (5), and found t o vary between 1.2 and 1.8 B.M. presumably because o f decomposition.
The presence o f
copper ( I I ) was t h e r e f o r e i n d i c a t e d . A d-d t r a n s i t i o n a t t r i b u t a b l e t o copper ( I I ) was observed at 20,500 on-1.
The F..S.R. spectr~n o f the bulk s o l i d at 25°C c o n s i s t e d
o f a n o n - i s o t o p i c d e r i v a t i v e curve, with gl = 2.089 and g2 = 2.148. The i n f r a r e d spectrum of B contained no N-H s t r e t c h i n g or bending modes.
Bands at 12~0 on-1 and 1085 an -1 a t t r i b u t a b l e t o ~as(NSO)
and vs (NSO) in the ligand A were s h i f t e d t o 1280 and 950 on-1 respectively.
Bands a t 527 and 285 an -1 are assignable t o Cu-N
s t r e t c h i n g modes. Ethylene di~nine (en) r e a c t e d with B in dry benzene t o produce Cu(en) (PhM~SO)2. This compound was extremely unstable in a i r .
On
the basis o f the above o b s e r v a t i o n s , we conclude t h a t Compound B i s probably a pyr~nidal square-planar complex, with copper bonded t o the oxygen and n i t r o g e n atoms adjacent to the benzene r i n g s , water occupying an a x i a l p o s i t i o n . Mercury ( I I ) a c e t a t e r e a c t s in a q u a n t i t a t i v e manner under s i m i l a r r e a c t i o n conditions to form Hg(PhNNSO)2, a b r i g h t yellow compound o f s a t i s f a c t o r y analysis which decomposed e x p l o s i v e l y at 69°C.
This complex possesses an n ÷ r
bond a t 27,700 an -1.
I n f r a r e d bands assignable e s s e n t i a l l y t o ~as(NSO) and ~s (NSO) occur a t 1288 and 10(]O on -1 r e s p e c t i v e l y .
Mercury-nitrogen v i b r a t i o n s
are found at 280 and 255 an -1. Caution must be e x e r c i s e d in the r o u t i n e handling o f these ccmrpounds due t o t h e i r tendency t o detonate.
Vol. 7, No. 8
COMPLEXES OF Cu(Ii) AND HI~Ii)
References 1.
N. COLLINS and W. K. GLASS, Chron. CAlm., 211(1967).
2.
W. VERBEEK and W. S l ~ ,
Angew. Chin. internat, ed.
8_, 376(1969). 3.
P.W. ROBINSON and A. WOJCICK, Chest. Comm., 951(1970).
4.
S. OTSUI(A, T. YOSHIDA, and A. NAKAMIJRA, Inorg. Chem., 7,
1833(1968). S.
A. M I ~ I S ,
6.
H . P . FRITZ and K. E. SOIRARZHA~, J. Orgmlometal. Chem., 1_, 2OS(1963).
Bet., 2_22, 2228(1889).
7,35