Solid State Communications, Vol. 28, pp. 10011004.

Pergamon Press Ltd. 1978. Printed in Great Britain.

X-RAY ABSORPTION SPECTRAL INVESTIGATIONS ON MIXED-VALENCE

COPPER COMPLEXES OF PENICILLAMINE AND CYSTEAMINE
H.L Nigam
Department of Chemistry, University of Allahabad, Allahabad-21 1002, India
B.D. Srivastava
School of Studies in Physics, Vikram University, Ujjain-45601 0, India
and
J.Prasad
School of Studies in Chemistry, Vikram University, Ujjain-45601 0, India
(Received 24 July 1978 by MF. Collins)

The X-ray K-absorption spectra of copper in some of its complexes

involving ligands like penicifiamine (known detoxicating agent for heavy
metal poisoning) and cysteamine (a known radiation protector) have been
investigated using a 4.0cm curved crystal spectrograph. These complexes
are described in the literature as being mixed-valence [1, 21. The copper
penicillamine complex shows two distinct edges, K1 and K2, indicating
mixed-valency in the complex. The cysteamine complexes do not show
any splitting of the edges. In one of the cysteainine complexes, which is
said to involve molecular oxygen, the magnitudes of shifts of the main
edge and principal absorption maximum fall close to copper (II) compounds whereas in the other complex, these shifts are in the range of
copper (I) compounds. The probable reasons for the observed deviations
have been discussed.
1. INTRODUCTION
RECENTLY redviolet coloured complexes supposed

penicillamine and cysteamine (Table 1) described by

Tanaka et al. [1, 2] with regard to their isolation and
characterisation.

to contain copper m the mixed-valence state using

ligands like penicillamine [1] and cysteamine [2] have
been reported on the strength of stability constants,
electronic, i.r. and PMR spectral measurements. The
penicillamine is a well-known detoxicating agent for
heavy metal poisoning and the cysteamine is a good
radiation protector. The mechanism of the biochemical
functions of these thiol ligands may involve formation
of the mixed disulphide [3] and chelate formation [4]
as important factors, but the results so far described
lack evidence which confirm the mixed-valence state in
a physical sense. Also, considering the theoretical
aspects [5], the mixed-valence systems offer a class of
compounds unique in chemistry.
X-ray spectoscopy for chemical analysis (XSCA)
which has emerged, in recent years, as a powerful tool
for the study of coordination compounds [69],may
provide an unambiguous answer to the vexed question
of the valence state in such compounds. Very little
X-ray spectroscopic work has been done to date on the
mixed-valence compounds. From the above-mentioned
stand point, we have therefore attempted X-ray absorption investigations on copper complexes with

2 EXPERIMENTAL

1001

X-ray absorption studies were carried out on a

Machlett sealed X-ray tube with a tungsten target which
was operated at 16 kV and 7 mA. A 40 cm Cauchois
type curved crystal spectrograph using (100) reflection
planes of mica for the analyser was employed to record
the spectra on Agfa Curix Ml. X-ray films. The set up
was standardized by resolving the MoK,~, doublet in
the first order which gave dispersion of about 12 XU
mm~.Tungsten La,, La2, L~,and L~emission lines
were taken as reference lines for the measurements.
The wavelengths of these line were taken from the
standard table of Bearden [10]. The absorption screens
were prepared by evenly spreading the substances in
fine powder form on Scotch tape. Suitable thin screens
were prepared and were placed between the X-ray tube
window and the analysing crystal. The exposure time
varied from 4 to 6 hr. Several spectrograms were taken
on a Carl-Zeiss GIl microphotometer coupled with
Carl-Zeiss G lB 1 recorder with magnification 100 x for
each sample.

1002

INVESTIGATIONS ON MIXED-VALENCE COPPER COMPLEXES

Vol. 28, No.12

Table 1. Colour, PH of isolation and spectral data ofmixedvalence copper complexes with penicillamine and
cysteamine
Complex

Ligand

Colour

of Ligand
to metal
tion
ratio

Spectral evidence
is.

C,0H,~04S2N3Cu~2H2OViolet
[I]

6.2

1: 1

C4H,402S2N3CU3C14
[II]

Redviolet

34

2:

Redviolet

78

1: 1

PH

Reference

isolaPenidilamine

Cysteamine

Electronic

Presence of
absorption
and
845 an~
bandsat
885 due
to 0-0 stretching
vibrations.

Intensificetion of
absorption band at
520Mm
Intensification of
480Mm band at
absorption

[1)

Intensification of
absorption band at
420Mm

[2]

[2]

C
4H,2S2N2Cu3C14
[III]

Table 2. Shifts in the K-absorption edge, the relative energies ofprincipal absorption maxima in copperpenicillamine
and coppercysteamine complexes (in eV)
Complex

Xk(XU)

0.05

C,0H,,02S3N3Cu3-2H20
[I]
C4H,402S2N3Cu2C14
[II]
C4H,2S2N3Cu3C14
[III]
ax

K,

XK(metai) =

AK2

1377.23a

(vfR)K

(Av/R)x

~E

0.6

(~P/R)A

EA 0.6

1376.66
l375.l9~
1374.93

661.94
662.65
662.78

0.51
1.22
1.35

6.92
16.56
18.32

1376.22

662.16

0.73

9.90

0.05

1376.54

661.67
662.23
662.00

0.24
0.80
0.57

3.26
10.86
7.74

1377.41

661.58

0.15

2.04

1376~07b

(v/R)A

XA(XU)

CX

1377.73 X.U.
3. RESULTS AND DISCUSSION

complexes in the coppercysteamine complex, [II].

Surprisingly, however, the magnitudes of the edge shift
The K-absorption spectra of copper in the cornand the peak shift fall close to copper (I) complexes in
plexes studied are shown in Fig. 2. The energy scale is
the copper cysteamine complex [III]. All these red
based on the first inflection point of the metallic Kviolet coloured complexes, [I], [II] and [1111containing
absorption edge as zero in the usual manner. The shifts
copper in the mixed valence state have been characterin the absorption edge (~E)and the energy of the
ised on the basis of stability constants, visible and
principal absorption maximum (EA) of copper in these
ultraviolet, i.r. and PMR spectral measurements [1, 2].
complexes are given in Table 2. The copper
Some other sulphur-containing ligands like meroaptopenicillamine complex [I] shows two distinct absorpacetic acid [13], thiomalic acid [14] and thiovanol [15]
tion edges, K1 and K2 (Fig. 2) corresponding to the
are also known to give redviolet coloured mixedvalence states Cu(I) and Cu(II) respectively. The energy
valence copper complexes. The bonding arrangement in
separation between the absorption maxima, A1 and A2
these complexes ([II, [II] and [LIIITable 1) have been
(assigned as ls -+ 4p~transitions corresponding to Cu(I)
shown [1, 2] to be as given in Fig. 1.
and Cu(II) respectively) is 9.6 eV (Table 2) which is in
The complex [II] has been shown [2] to involve
fair agreement with the observations of Beeman et aL
molecular oxygen on the basis of ~r. spectrum
1 (appeardue to
[11].
This
type
of
splitting
of
the
absorption
edge
was
ance
of
absorption
bands
at
885
and
845
cm
also observed in the mixed-valence copperthiomalic
00 stretching vibrations) and elemental analyses and
acid and copperthiovanol complexes [121.The copper it was assumed that one electron is taken from copper
cysteamine complexes [II] and [HI] do not show any
(I) by 02 to give O~as perhydroxyl ion and then one
splitting of the absorption edges. Further, shifts in the
copper (I) is converted into copper (II) to give the
main edge as well as in the principal absorption maxicomplex [II] in which the molecular oxygen is absorbed,
mum (Table 2) fall close to the values for copper (II)

Vol. 28, No.12

INVESTIGATIONS ON MIXED-VALENCE COPPER COMPLEXES

1003

HIC\
CCH

H3CI
~<CU
~Cu(I)~
Ch

n~

H3N cH2cH2scul
H3~CH2CH2S~u(II)

H3CNI

i~ ~\
0

H3C

[II]
I-

Ui
>

I~

A2
A

CH5CH2

[II]

II ~~S~c~I)
Cu(II)

[iiiJ

I~lH~

CH~CH2

[ni]

_____________________

Fig.
1. The
bonding arrangement
[I] and
coppercysteamine
[II] in
andcopperpenicillamine
[HI] complexes.

0 spectra
10 20(eV)
30mixed-valence
Fig. 2. X-ray absorptionENERGY
of

copperpenicillarnine [I] and coppercysteamine [II]

although no direct evidence of the existence of molecular and [Ill] complexes.
oxygen in the complex has been obtained. The same
electronic charge over all atoms to which they are
authors have also made a significant observation that
bound [18]. Hoim et al. [19] have shown this effect in
copper complexes of cysteamine are relatively unstable
Fe4S4(SR)4 clusters involving Fe(II) and Fe(Ill). No
in comparison to copperpenicillamine complex. Even
technique has allowed Fe(ll) to be distinguished from
if the mixed-valence complexes of copper are formed
Fe(III). Several factors, such as low-lying empty
with cysteamine as claimed by Tanaka et al. [2] there
d-orbitals, high polarizability, shallowness of the potenis a definite possibility of their decomposition and subtial energy minimum along the MS coordinate, and
sequent aerial oxidation on long keeping and extended
others, must contribute to this levelling of ion charge
exposure to X-ray under the conditions of our expertproduced by sulphur atom ligands. Recently, ESCA ment. The so-called oxygen carrying cysteamine cornstudies [2023]of the rhenium 4f512,712 binding energies
plex [II], thus shows only the copper (II) edge after
in some compounds have also failed to give a distinct
exposure to X-rays. In the case of copperchelate ~
correlation between oxidation state and binding energy
the formulation by Tanaka et aL [2] seems to be incomand it was concluded that in a low oxidation state, the
plete at least with regard to the coordination number of
effective nuclear charge at the metal center changes
copper (II) and the charge on the complex. No analyses
little with change in oxidation state. Furthermore, the
for metal and sulphur content and magnetic suscepticluster structures found for certain complexes are
bility measurement have been reported for these comclearly favourable for the delocalization of charge over
plexes. The observed instability of the complex [IH]
many centers and this perhaps provides an additional
may also include the possibility of photo-reduction [16]
explanation of the absence ofmetal-core binding energy
of the cupric ion by X-rays in this complex.
shins
The problem of ambiguity in the assignment of
correct oxidation states [17] and electronic structures
Acknowledgement Grateful thanks are due to Prof.
has long been associated with the reducing character of
H. Tanaka (Faculty of Pharmaceutical Sciences, Kyoto
ligands like dithiols and dithiones. Sulphur ligands, in
University, Japan) for providing the samples of comgeneral, are very effective in their ability to average the
plexes investigated here.

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1004

INVESTIGATIONS OF MIXED-VALENCE COPPER COMPLEXES

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