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446

Yugeng

Transition Metal Chemistry, 19 (1994) 446-448

Spectral and thermal properties of saccharin and saccharin metal


complexes
Zhang Yugeng
Department of Applied Chemistry, University of Science and Technoloqy of China, Hefei, Anhui, 230026, P.R. of China
Summary
The photoacoustic spectra, i.r. spectra and d.t.a, curves of
saccharin (o-sulphobenzoimide) and its transition metal
complexes have been studied. It was found that saccharin,
as a ligand, has three coordination modes (monodentate,
q2-bridging or r/2-chelating) and it can also act as a free
anion without coordinating to the metal. The charge
transfer spectra of saccharin and its complexes have also
been studied; the results can be correlated with the coordination mode.

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

at a frequency of 12 Hz. The sample was placed in a locally


built photoacoustic cell fitted with an E R M l0 electret
microphone. The output signal was normalized for changes
in lamp intensity using a carbon-block reference, and
displayed and resolved by computer.

Results and discussion


Coordination natures
Saccharin has variable coordination characteristics as a
ligand. It usually coordinates to a metal through the
nitrogen atom, in complexes such as [,M(Sac)z(H20)4 ].
2 H 2 0 [,M = Fe, Co, Ni, Cu or Mn, Figure 1, (I)]. It can
also utilize the carboxyl oxygen to bridge two metals
[-Figure 1, (2)] as in [,Cuz(Sac)4(Im)4] ~1~ or chelate to a
single metal [-Figure 1, (3)]. This latter chelating mode
is found in rare earth saccharin complexes, presumably
because of the large coordination numbers and large ionic
radii. Saccharin may exhibit two coordination modes in
one complex; in I-Cu(bipy)z(Sac)]'(Sac)'3HeO, one saccharin molecule exists as an anion without coordination
and the second coordinates to the metal via the nitrogen.
In [-Cuz(Sac)4(Im)4] two saccharins coordinate by mode
( I ) and the rest by mode (2), forming a [ - - M 1 N - CzO--M2--N--C--O
- ] octagonal ring. To date,
examples of coordination through the oxygen atoms of
the SO2 group have not been found. The spectrochemical
order of saccharin in transition metal complexes is:
imidazole > saccharin > water (12~.

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-

Transition Metal Chemistry, 19 (1994) 446 448

Saccharin complexes

osc_o
,.,~/\ /--)

(1)

M'

(2)

(3)

Figure 1. The observed coordination modes of saccharin complexes.


(Sac)].(Sac)'3H20 has only one absorption in this region,
presumably because the ionic saccharin group is hydrated
and the extensive hydrogen bonding may surpress the
v ( C z O ) absorption. In those complexes where saccharin
coordinates to the metal by both modes (1) and (2), or
by mode (3), such as [Cu2(Sac)g(Im)4 ] and Euz(Sac)3(NO3)3.12H20, the C ~ O absorption is multiply split
and appears at 1660-1610cm-1. It is clear that the red
shift of v ( C z O ) in coordination modes (2) and (3) is
larger than that of coordination mode (1). For example,
the red shift for La(Sac)z.4H20 is only 80 cm-1, and this
complex has coordination mode (1) in its crystal structure.
The intensities of the C - - N and N - - S O 2 stretching
absorptions of all the coordinated saccharin groups are
larger than those of the free saccharin molecule. In all the
spectra of the complexes, the i.r. absorptions of the SO 2
group show no significant change, consistent with the fact
that this group is not coordinated in any of the complexes.

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

o 2 2802 + 2CO2 + (1/2)N2

(2)

Charge transfer spectra


The saccharin molecule contains a strongly conjugated
system which tends to give charge transfer absorptions
(LMCT). The photoacoustic (p.a.) spectra of free saccharin,
its sodium salt and [M(Sac)2(HzO)4]'2H20 in the region
of 300-500 nm are presented in Table 1. The p.a. spectrum
of saccharin shows a strong absorption below 310nm
which may be assigned to a L --* L* transition. This band
is also present in the p.a. spectra of the metal complexes,
as shown in Table 1, without any evident shift. However,
in the spectrum of the sodium salt, the observed strong
absorption at 330 nm is assigned to the L--, L* transition
with a red shift of 20nm. This result highlights the difference between the coordinate and ionic bonds (14).
In transition metal saccharin complexes, the M - - , L
charge transfer bands may occur over a wide wavelength
region. For the divalent transition metal ions, copper(II)
is most likely to be photoreduced, nickel(II) and cobalt(II)
to be photostable, whilst iron(II) and manganese(II) may
be photooxidized. It is presumably for this reason that in
the EM(Sac)2(H20)4]'2H20 (M = Mn, Co, Fe, Ni or Cu)
complexes, only for the iron(II) and manganese(II) complexes may M--*L charge transfer bands be observed,
associated with the d(M) ~ zc*(L) transition (the bands are
at 413 and 370 nm for the iron and manganese complexes,
respectively). The band at 340 nm in the spectrum of the
copper(II) complex is assigned to L ~ M charge transfer,
from an occupied ligand z-orbital to the empty d-orbital
of copper(II). No charge transfer bands are observed in
the nickel(II) and cobalt(II) complexes at wavelengths
greater than 300 nm (15).
Table 1 shows the p.a. spectra of some other saccharin
complexes in the region of 300-500 nm. In the spectrum
of [Cu2(Sach(Imh] the charge transfer 7r ~ d absorption
is very strong and has a large red shift, suggesting that the
coordination interaction of this complex is strong. As for

Table 2. D.t.a. data for saccharin and its complexes (~


Compound

H20 Alcohol Saccharin

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.

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Transition Metal Chemistry, 19 (1994) 446-448


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(Received 17 August 1993)

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