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Reactivity of Labile Triosmium Complexes, Os3(CO)10(MeCN)2 and Os3(CO)10(µ-H)2 with Tetraethylthiuram Disulfide (Disulfiram)
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Reactivity of Labile Triosmium Complexes, Os3(CO)10(MeCN)2 and Os3(CO)10(µ-H)2 with Tetraethylthiuram Disulfide (Disulfiram)
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Reactivity of Labile Triosmium Complexes, Os3(CO)10(MeCN)2 and Os3(CO)10(µ-H)2 with Tetraethylthiuram Disulfide (Disulfiram)
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Journal Article
Reactivity of Labile Triosmium Complexes, Os3(CO)10(MeCN)2 and Os3(CO)10(µ-H)2 with Tetraethylthiuram Disulfide (Disulfiram)
2025
Overview
Reactions of the anti-alcohol drug disulfiram (tetraethylthiuram disulphide = Et
4
TDS) with low valent triosmium complexes are described. Room temperature reaction with [Os
3
(CO)
10
(MeCN)
2
], affords three new open polynuclear clusters, [Os
3
(CO)
10
(S
2
CNEt
2
)
2
] (
1
), [Os
4
(CO)
12
{µ
3
-η
1
(C),
κ
2
(O,O)-CO
2
}(S
2
CNEt
2
)(µ-S
2
CNEt
2
)] (
2
) and [Os
3
(CO)
9
(µ
3
-SCNEt
2
){µ-SC(O)NEt
2
}] (
3
) together with the known mononuclear complex
cis-
[Os(CO)
2
(S
2
CNEt
2
)
2
] (
4
). All result from oxidative-addition of disulfiram to the triosmium centre, with
2
also capturing CO
2
, while cluster
3
has undergone further C–S bond scission and partial oxidation of one of the generated thiocarboxamide ligands. With [Os
3
(CO)
10
(µ-H)
2
], complexes
1
and
4
are also formed along with previously reported [Os
3
(CO)
10
(µ-S
2
CNEt
2
)(µ-H)] (
5
), [Os
3
(CO)
9
(µ
3
-S
2
CNEt
2
)(µ-H)] (
6
), and the new cluster, [Os
3
(CO)
9
(µ-S
2
CNEt
2
)(µ-H)] (
8
), which is an isomer of
6
. The product distribution is rationalized by completing pathways following the oxidative-addition of disulfiram. Thus, reductive-elimination of H
2
affords
1
, which in turn converts to
4
, while reductive-elimination of the (unstable) dithiocarbamic acid, Et
2
NCS
2
H, leads to the formation of
5
, which can further lose CO to afford isomers
6
and
8
. Heating disulfiram with [Os
3
(CO)
12
] at 110 °C predominantly affords
4
, together with smaller amounts of the novel trithiocarbamate complex,
cis-
[Os(CO)
2
(S
2
CNEt
2
)(S
3
CNEt
2
)] (
9
). All the compounds have been characterized by elemental analysis, IR and
1
H NMR spectroscopy, together with single crystal X-ray diffraction analysis of six molecules.
Publisher
Springer US,Springer Nature B.V
Subject
