Reactivity of Labile Triosmium Complexes, [Os₃(CO)₁₀(MeCN)₂] and [Os₃(CO)₁₀(µ-H)₂] with Tetraethylthiuram Disulfide (Disulfiram)

TY - JOUR

T1 - Reactivity of Labile Triosmium Complexes, [Os3(CO)10(MeCN)2] and [Os3(CO)10(µ-H)2] with Tetraethylthiuram Disulfide (Disulfiram)

AU - Bhoumik, Nikhil C.

AU - Huda, Md Nazmul

AU - Nesterov, Vladimir N.

AU - Hogarth, Graeme

AU - Kabir, Shariff E.

AU - Sarker, Jagodish C.

N1 - Publisher Copyright: © The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2024.

PY - 2025/2

Y1 - 2025/2

N2 - Reactions of the anti-alcohol drug disulfiram (tetraethylthiuram disulphide = Et4TDS) with low valent triosmium complexes are described. Room temperature reaction with [Os3(CO)10(MeCN)2], affords three new open polynuclear clusters, [Os3(CO)10(S2CNEt2)2] (1), [Os4(CO)12{µ3-η1(C),κ2(O,O)-CO2}(S2CNEt2)(µ-S2CNEt2)] (2) and [Os3(CO)9(µ3-SCNEt2){µ-SC(O)NEt2}] (3) together with the known mononuclear complex cis-[Os(CO)2(S2CNEt2)2] (4). All result from oxidative-addition of disulfiram to the triosmium centre, with 2 also capturing CO2, while cluster 3 has undergone further C–S bond scission and partial oxidation of one of the generated thiocarboxamide ligands. With [Os3(CO)10(µ-H)2], complexes 1 and 4 are also formed along with previously reported [Os3(CO)10(µ-S2CNEt2)(µ-H)] (5), [Os3(CO)9(µ3-S2CNEt2)(µ-H)] (6), and the new cluster, [Os3(CO)9(µ-S2CNEt2)(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 H2 affords 1, which in turn converts to 4, while reductive-elimination of the (unstable) dithiocarbamic acid, Et2NCS2H, leads to the formation of 5, which can further lose CO to afford isomers 6 and 8. Heating disulfiram with [Os3(CO)12] at 110 °C predominantly affords 4, together with smaller amounts of the novel trithiocarbamate complex, cis-[Os(CO)2(S2CNEt2)(S3CNEt2)] (9). All the compounds have been characterized by elemental analysis, IR and 1H NMR spectroscopy, together with single crystal X-ray diffraction analysis of six molecules.

AB - Reactions of the anti-alcohol drug disulfiram (tetraethylthiuram disulphide = Et4TDS) with low valent triosmium complexes are described. Room temperature reaction with [Os3(CO)10(MeCN)2], affords three new open polynuclear clusters, [Os3(CO)10(S2CNEt2)2] (1), [Os4(CO)12{µ3-η1(C),κ2(O,O)-CO2}(S2CNEt2)(µ-S2CNEt2)] (2) and [Os3(CO)9(µ3-SCNEt2){µ-SC(O)NEt2}] (3) together with the known mononuclear complex cis-[Os(CO)2(S2CNEt2)2] (4). All result from oxidative-addition of disulfiram to the triosmium centre, with 2 also capturing CO2, while cluster 3 has undergone further C–S bond scission and partial oxidation of one of the generated thiocarboxamide ligands. With [Os3(CO)10(µ-H)2], complexes 1 and 4 are also formed along with previously reported [Os3(CO)10(µ-S2CNEt2)(µ-H)] (5), [Os3(CO)9(µ3-S2CNEt2)(µ-H)] (6), and the new cluster, [Os3(CO)9(µ-S2CNEt2)(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 H2 affords 1, which in turn converts to 4, while reductive-elimination of the (unstable) dithiocarbamic acid, Et2NCS2H, leads to the formation of 5, which can further lose CO to afford isomers 6 and 8. Heating disulfiram with [Os3(CO)12] at 110 °C predominantly affords 4, together with smaller amounts of the novel trithiocarbamate complex, cis-[Os(CO)2(S2CNEt2)(S3CNEt2)] (9). All the compounds have been characterized by elemental analysis, IR and 1H NMR spectroscopy, together with single crystal X-ray diffraction analysis of six molecules.

KW - Carbon–sulfur bond scission

KW - Disulfiram

KW - Dithiocarbamate

KW - Molecular structures

KW - Osmium cluster

KW - Oxidative-addition

KW - Trithiocarbamate

UR - https://www.scopus.com/pages/publications/85218113954

U2 - 10.1007/s10876-024-02749-z

DO - 10.1007/s10876-024-02749-z

M3 - Article

AN - SCOPUS:85218113954

SN - 1040-7278

VL - 36

JO - JOURNAL OF CLUSTER SCIENCE

JF - JOURNAL OF CLUSTER SCIENCE

IS - 1

M1 - 34

ER -