Z. anorg. allg. Chem. 600 (1991) 31-35 J.A.

Barth, Leipzig

Photooxidation of Transition Metal Complexes of

1,3-Dithiole-2-thione-4,5-dithiolate (dmit) and
1,2-DithioIe-3-thione-4,5-dithiolate (dmt)
W. DIETZSCH*, OLK
RUTH-MARIA
L e i p z i g , University, Department of Chemistry

J. P. PUAUX
S a i n t - E t i e n n e (France), Universite Jean Monnet

Dedicated to Professor Eberhard Hoyer on his 60th Birthday, May 26th, 1991

A b s t r a c t . Metall(I1) bis-chelates of 1,3-dithiole-2-thione-4,5-dithiolate(dmit) and

1,2-dithiole-3-thione-4,5-dithiolate (dmt) undergo in CHCl,/CH,CN (ratio 1 :24) photooxidation to
the metal(II1) bis-chelates when irradiated at 313 nm. No side reactions were observed. There is no
correlation between the quantum yields of photooxidation and the electrochemical halve-wave poten-
tials. This holds also in comparison to maleonitriledithiolato chelates.

Photooxidation von Ubergangsrnetall-Komplexen mit 1,3-Dithiol-2-thion-4,5-dithiolat

(dmit) und 1,2-Dithiol-3-thion-4,5-dithiolat(dmt)
I n h a 1t s u b e r s i c h t. Metall(I1)-Bis-Chelate des 1,3-Dithiol-2-thion-4,5-dithiolats
(dmit) und
1,2-Dithiol-3-thion-4,5-dithiolats (dmt) werden durch Bestrahlung bei 313 nm in CHCl,/CH,CN
(Verhaltnis 1 :24) zu den Metall(II1)-Bis-Chelaten photooxidiert. Es werden keine Nebenreaktionen
beobachtet. Es gibt Korrelation zwischen den Quantenausbeuten der Photooxidation und den
elektrochemischen Halbstufenpotentialen. Das gilt auch fur den Vergleich mit Maleonitrildithiolat-
Chelaten.
K e y w o r d s : Photooxidation - transitional metal complexes - 1,2-dithiole-3-thione-
4,Sdithiolate - 1,3-dithiole-2-thione-4,5-dithiolate

1. Introduction
Coordination compounds with chalcogen-rich heterocyclic dichalcogenolene ligands
cause not only interesting solid state conductivity [I] or magnetism [2] properties depend-
ing on the connected cation, but show also remarkable solution redox behavior. As ex-
pected for dichalcogenolene complexes, reversible one-electron redox reactions (1) have
been generated chemically and electrochemically [3, 41:
[M(dichalcogenolene 1igand)J- G [M(dichalcogenolene ligand),]- + e- (1)
where “dichalcogenolene ligand” means dmit or dmt. Both the reduced and the oxidiz-
ed form as well can be isolated using suitable cations. Further one-electron oxidation
to neutral species (containing formally metal(1V)) is not reversible because low-soluble
32 Z. anorg. allg. Chem. 600 (1991)

solids with complicated stoichiometry occur during the chemical or electrochemical oxi-
dation. The oxidation according to (1) can be achieved also by photolysis, exhibiting
quantum yields strongly dependent on the used wavelengths. Up to now the real
mechanism of photooxidation is not completely clear [5, 61. However, the presence of
halocarbons as electron acceptors is obviously necessary. Quantum yields are influenced
by the relative redox potentials of the halocarbons. We investigated the photooxidation of
a series of metal(I1) compounds containing the ligands dmit and dmt:

M = Cu. Ni, Pd. Pt M Ni

2. Experimental
Ligands and complexes as tetrabutylammonium salts were prepared as described before [3,4]. Light
source for the room temperature photooxidation reactions was an Osram 250 W mercury lamp. Irradia-
tion wavelength of 313 nm was selected using a Bausch and Lomb monochromator. Photolysis was car-
ried out in 1 cm spectrophotometer cells. Absorbed light intensities were determined by ferrioxalate ac-
tinometry. Reactions were monitored with a Perkin-Elmer 552 spectrophotometer. Quantum yields were
calculated using a decreasing band of the dianion and an increasing band of the monoanion and cor-
rected for the inner-filter effect.

3. Results and Discussion

The results differ remarkably from those found for maleonitriledithiolato or
1,2-diphenylethylene-I,2-dithiolato complexes. Despite a drastically reduced portion of
CHCl, in the used solvent mixture (CHCl,/CH,CN = 1 :24, in contrast to 24 : 1 used by
Dooley and Patterson [6]), the irradiation times had to be shortened considerably to get
useful results as can be seen from Fig. 1 and Fig. 2 in comparison to irradiation times used
for the former compounds [5,6]. We did not observe any spectral change when irradiating
at wavelengths longer than 350 nm. Because all complexes exhibit strong absorption
bands around 300 nm, the 3 13 nm line of the mercury lamp was chosen for irridation. In
contrast to the maleonitriledithiolato complexes [6], we could not observe any side reac-
tion in the case of complexes under study. The reactions proceed smoothly exhibiting
clear isosbectic points. Fig. 1 and Fig. 2 display the spectral changes during photolysis of
[Cu(dmit),12- and [Ni(dmit),I2-. In both cases the spectra of the final products of
photooxidation, [Cu(dmit),]- and [Ni(dmit),]-, respectively, are added. Both complexes
could be isolated purely as tetrabutylammonium salts after chemical oxydation of the
metal(I1) complexes [3].
As can be seen from the Table 1, the comparison of the photooxydation reactions of
dmit or dmt complexes and mnt complexes is not simple. There is no correlation between
quantum yields for complexes containing equal metal ions but different ligands. Obvious-
ly, depending on the ligand system different reaction mechanisms go off. This assump-
tion is confirmed by the fact that only dmit complexes show a strong solvatochromic ef-
fect because of the presence of the C = S group [7]. If a CTTS (charge transfer to solvent)
 et. al., Photooxidation of Transition Metal Complexes
W. DIETZSCH 33

I\ ,-

final product CCu(dmit)21-

I I I I I I

300 400 SO0 600 I00 800 XCnml

Fig. 1 Spectral changes during photooxidation of [Cu(dmit),]’-; c = 5 . 4 ~lo-’ M in CHCl,/CH,CN

(I :24); in each case spectra were taken after 1 min irradiation (313 nm).

I \J( \ final product CNi(dmitIp1-

Fig. 2 Spectral changes during photooxidation of [Ni(dmit),]’-; c = 3 . 5 ~lo--’ M in CHCI,/CH,CN

(1 :24); in each case spectra were taken after 1 min irradiation (313 nm).
34 Z. anorg. allg. Chem. 600 (1991)

Table 1 Comparison of quantum yields of photooxidation of [M(dmit)z]2- in 24: 1 (v/v)

CH3CN/CHC13and [M(mnt)z]2- in I :24 (v/v) CH$N/CHC13 and electrochemical half-wave poten-
tials [ML2]'- [ML$ + e- (in CHsCN vs. SCE)
Complex ~313 Ref. EiN) Ref.

M = Ni 0.12 ") -0.19 [31

Pd 0.30 ") -0.09 [31
Pt 0.16 ") -0.27 [31
cu 0.04 ") -0.07 [31

0.04 ") -0.07 141

M = Ni 0.25 151 0.23 181

Pd 0.12 151 0.46 [81
Pt 0.23 [51 0.21 181
cu b, PI 0.34 [81

") This work.

b, No data given at 3 13 nm.

state, postulated by Vogler and Kunkely [ 5 ] , is true, one would expect that for reaction (3),
also postulated by these authors,
[ML2I2- + CHCI, + [ML,]- + C1- + 'CHCI, (3)
the influence of the concentration of CHC1, in the used solvent mixture is stronger on
dmit or dmt complexes than on mnt complexes. This gives an explanation for the easier
photooxidation of dmit and dmt complexes in solvent mixtures with drastically reduced
CHC1, concentration. Thus our results are consistent with reaction way (3).
We could not find any correlation between the electrochemical half-way potential and
the quantum yield. Despite dmit and dmt complexes are oxydized easier than mnt com-
plexes, it was impossible to verify the expectation [5] that such complexes are photosen-
sitive at wavelengths longer than 350 nm.

References
[I] KOBAYASHI, A.; KIM,H.; SASAKI,Y.; KATO,R.; KOBAYASHI, S.; NISHIO,Y.; KAJITA,K.;
H.; MORIYAMA,
SASAKI,W.: Chem. Lett. 1987, 1819.
W. DIETZSCH
et. al., Photooxidation of Transition Metal Complexes 35
[2] BRODERICK, W. E.; 'T~OMPSON, J. A.; GODFREY, M. R.; SABAT,M.; HOFFMAN, B. M.; DAY,F. P.:
J. Amer. Chem. SOC.111 (1989) 7656.
[3] STEIMECKE, G.; SIELER,H.-J.; KIRMSE, R.; HOYER,E.: Phosphorus Sulfur 7 (1979) 49.
[4] STEIMECKE, G.; SIELER,H.-J.; KIRMSE,R.; DIETZSCH, W.; HOYER,E.: Phosphorus Sulfur 12 (1982)
237.
[5] VOGLER, A.; KUNKELY, H.: Inorg. Chem. 21 (1982) 1172.
[6] DOOLEY, D. M.; PATTERSON, B. M.: Inorg. Chem. 21 (1 982) 4330.
[7] STEIMECKE, G.: Thesis, Univ. Leipzig, 1977.
[8] MCCLEVERTY, J. A.: Progr. Inorg. Chem. 10 (1968) 49.

Bei der Redaktion eingegangen am 19. September 1990.

Anschr. d. Verf.: Doz. Dr. WOLFGANG DIETZSCH, Dr. RUTH-MARIA OLK,

Sektion Chemie d. Univ., Talstr. 35, 0-7010 Leipzig, Bundesrepublik Deutschland
Prof. Dr. JEAN-PIERRE PUAUX,Univ. Jean Monnet, 23 Rue du Dr. Paul-Michelon,
Saint-Etienne Cedex 2, F-42023 (France)