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Yugeng
Introduction
The chemistry of saccharin (o-sulphobenzoimide, Sac),
commonly used as a non-nutritive sweeting agent, has
attracted attention in recent years due to its suspected
carcinogenic nature (1"2). Its transition metal complexes
are interesting because of their biological significance. The
biological activities of m a n y metal complexes are found
to vary with small changes in their composition and
configuration ~3). Notwithstanding, studies on general
physico-chemical properties of transition metal complexes
of saccharin are relatively scanty.
Some crystal structures of metal-saccharin complexes
have been determined in the last ten years (4'51. The
electronic absorption spectra and some other properties
have also been studied t6). A series of new saccharin
transition metal complexes have been synthesized and
their crystal structures and electronic absorption spectra
reported tv-9). In this work, the vibration spectra, charge
transfer (CT) spectra, thermal properties and coordination
modes of saccharin in a series of its metal complexes are
discussed.
Experimental
Synthesis
The syntheses and crystal structures of [M(Sac)z(H20)4 ]"
2 H 2 0 (M = Fe, Co, Ni, Cu Or Mn) have been reported by
Haider et al/4'5). The syntheses and crystal structures of
[-Cuz(Sac)4(im)4](10), [,Cu(bipy)2(Sac)].(Sac).3H2 O(11} and
[,M(Im)4(HzO)2].(Sac)2 (M = Ni o r C o ) (9'12) have been
reported by this group, where the rare earth complexes,
La(Sac)z.4H20 , Euz(Sac)3(NO3) 3.12HzO and YCus(Sac)8(C2H50)2(OH)3" 5 H 2 0 have also been synthesized, their
spectral and thermal properties were determined (13). The
results of elemental analyses of all the samples were in
agreement with their formulae.
Characterization
I.r. spectra of the complexes were recorded in reflectance
mode, using KBr as the diluent on a Sakara-440 spectrometer. Photoacoustic spectra were recorded in the region
of 300 800 nm. The excitation source was a 500 W Xenon
lamp modulated by a variable speed mechanical chopper
0340-4285 9 1994 Chapman& Hall
I.r. spectra
The i.r. spectrum of saccharin can be divided into three
distinctive regions. High energy bands at 3420, 3020, 2980
and 2700cm -1 correspond to vas(C H), vs(C--H),
v s ( N - - H ) and Vas(N--H), respectively. In the middle
energy range, a band at 1720 c m - 1 corresponds to C = O
stretching, whilst bands at 1600 and 1462cm -1 are
assigned to C C stretching of the benzene ring. Three
bands at 1340, 1300 and 1181cm 1 correspond to the
stretching vibrations of the - - S O 2 - - N - - group.
The free saccharin anion has more than ten i.r. active
fundamentals of which the stretching modes of C - - O ,
C - - N and N H have been employed for structural
studies. The strong N - - H stretching absorption in the
spectrum of free saccharin is absent in the spectra of the
complexes, consistent with loss of a proton and coordination of the saccharin anion through nitrogen. Coordination through the carboxyl group is accompanied by a
red shift in v(C--O); these shifts, Av, for complexes with
various coordination modes are reported in Table 1. For
[M(Sac)2(H20)4]'2H20 (M = Cu, Ni, Fe, Co or Mn)
there are two v(C--O) absorptions with a small separation
of about 25cm -1. This is consistent with the crystal
structures, which show that the two coordinated saccharin
groups are in slightly different environments. [Cu(bipy)2-
Saccharin complexes
osc_o
,.,~/\ /--)
(1)
M'
(2)
(3)
Thermal properties
The d.t.a, data for free saccharin, [Cu(Sac)2(H20)4]'2H20
and YCus(Sac)s(CzHsO)z(OH)3.5H20 are presented in
Table 2. The free saccharin molecule decomposes at
200 70 ~ C. Upon coordination to a metal, the decomposition temperature of the saccharin anion is increased
to 300-400 ~ C. The complex [Cu(Sac)2(H20)4].2H20 is
a hydrate, and the water molecules are lost on heating to
90-150 ~ C. The water molecules of YCus(Sac)s(CzH s O)2(OH)3"5H20 are lost at 80-100~
whilst the alcohol
molecules of this complex are lost at 260 ~ C.
In Table 2, the coordinated saccharin group decomposes
in two steps. We suggest that these are as follows:
(C6H4)CONSO2
o2, C O N S O 2 + 6CO 2 + 2 H 2 0
(1)
2CONSO2
447
(2)
Saccharin
[Cu(Sac)z(H20),~]'2H20
130
90
YCus(Sac)8(C2HsO)z(OH)3"5H20
260
270
310, 350
300, 350
Table 1. The carboxyl group i.r. frequencies (cm 1) and charge transfer absorptions (nm) of complexes
Compound
v(CzO)
Av
LMCT band
Assignment
Saccharin
Sodium saccharin
[Cu(Sac)z(H20)4]" 2H20
[Fe(Sac)z(H20)4]" 2H20
[Mn(Sac)2(H20)4]'2H20
[Ni(Sac)2(H20)4] 2 H 2 0
[Co(Sac)z(HgO)4]-2HzO
[Cu(bipy)z(Sac)]'(Sac). 3H20
La(Sac)z'4H20
Eu2(Sac)3(NO3)3"12H20
[Cuz(Sac)4(Im)4]
YCus(Sac)8(C2H5O)2(OH)3- 5H20
1720
1650
1650, 1675
1650, 1675
1650, 1675
1650, 1675
1650, 1675
1660
1640
1660 1605
1660-1610
1650
70
55
55
55
55
55
60
80
60 115
60-110
70
<310
330
340
413
370
<300
<300
400
< 300
330
410
350
L~L*
L --, L*
n~d
d~rc*
d --. rr*
L~L*
L-*L*
rc~ d
L --*L*
7r~d
7r~ d
~z~ d
448
Yugeng
Eu2(Sac)3(NO3)3.12H20 , europium(III)is a weakly photoreduced ion and the complex has a type (3) structure, so
charge transfer (n ~ d) is also observed for this complex,
see Table 1. However, lanthanium(II) is a photostable ion
and no new charge transfer band can be observed in the
spectrum of La(Sac)2'4H20. In the case of the heteronuclear yttrium-copper complex, yittrium(III) is photostable. Hence, the charge transfer band of this complex is
attributed to the photoreduced copper(II), though the
band is affected by the interactions between copper(II)
and yttrium(III) ions ~16).
Acknowledgement
We gratefully thank the National Nature Science Fund
of P.R. China for financial support.
References
m M.J. Allen, E. Bayland, C. E. Dukes, E. S. Horming and
J. (3. Watson, Brit. J. Cancer, 11,212 (1957).
(2) j. M. Price, G. G. Biava, B. L. Oser, E. E. Vogin, J. Steinfield
and H. J. Ley, Science, 167, 1131 (1970).
(3) S. Livigstone, lnorg. Chim. Acta, 19, 5 (1976).
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