Oxidative-addition of tetramethylthiuram disulfide (Me4TDS) and monosulfide (Me4TMS) at a triosmium centre: Generation of dithiocarbamate, trithiocarbamate, thiocarboxamide and amino-carbyne ligands

Md Nazmul Huda; Jagodish C. Sarker; Vladimir N. Nesterov; Graeme Hogarth; Shariff E. Kabir

doi:10.1016/j.jorganchem.2024.123252

Oxidative-addition of tetramethylthiuram disulfide (Me₄TDS) and monosulfide (Me₄TMS) at a triosmium centre: Generation of dithiocarbamate, trithiocarbamate, thiocarboxamide and amino-carbyne ligands

Md Nazmul Huda, Jagodish C. Sarker^*, Vladimir N. Nesterov, Graeme Hogarth, Shariff E. Kabir

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

Thermolytic reactions of [Os₃(CO)₁₂] with tetramethylthiuram disulfide (Me₄TDS) and tetramethylthiuram monosulfide (Me₄TMS) are described. While both afford the anticipated bis(dithiocarbamate) complex cis-[Os(CO)₂(S₂CNMe₂)₂] (1) as the major product, unexpected secondary products result in both cases. With Me₄TDS this is the trithiocarbamate-dithiocarbamate complex cis-[Os(CO)₂(S₂CNMe₂)(S₃CNMe₂)] (2) resulting (formally) from sulfur insertion into an Os-S bond. Heating 1 with further Me₄TDS did afford 2, albeit in small amounts and on a timeframe incompatible with its formation under the initial reaction conditions. From the Me₄TMS reaction, binuclear [Os₂(CO)₃(S₂CNMe₂)₂(µ-CNMe₂)(µ-SCNMe₂)] (3) is a secondary product. It contains dithiocarbamate, thiocarboxamide and amino-carbyne ligands, the last two resulting (formally) from the oxidative addition of a C-S bond in Me₄TMS. Both new complexes have been characterised by X-ray crystallography.

Original language	English
Article number	123252
Journal	JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume	1016
DOIs	https://doi.org/10.1016/j.jorganchem.2024.123252
Publication status	Published - 1 Aug 2024

Keywords

Carbonyl
Dithiocarbamate
Osmium
Oxidative-addition
Thiocarboxamide
Trithiocarbamate

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10.1016/j.jorganchem.2024.123252

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Huda, M. N., Sarker, J. C., Nesterov, V. N., Hogarth, G., & Kabir, S. E. (2024). Oxidative-addition of tetramethylthiuram disulfide (Me₄TDS) and monosulfide (Me₄TMS) at a triosmium centre: Generation of dithiocarbamate, trithiocarbamate, thiocarboxamide and amino-carbyne ligands. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1016, Article 123252. https://doi.org/10.1016/j.jorganchem.2024.123252

@article{5b8f82e3826a47a5a67b5e250a4d47d9,

title = "Oxidative-addition of tetramethylthiuram disulfide (Me4TDS) and monosulfide (Me4TMS) at a triosmium centre: Generation of dithiocarbamate, trithiocarbamate, thiocarboxamide and amino-carbyne ligands",

abstract = "Thermolytic reactions of [Os3(CO)12] with tetramethylthiuram disulfide (Me4TDS) and tetramethylthiuram monosulfide (Me4TMS) are described. While both afford the anticipated bis(dithiocarbamate) complex cis-[Os(CO)2(S2CNMe2)2] (1) as the major product, unexpected secondary products result in both cases. With Me4TDS this is the trithiocarbamate-dithiocarbamate complex cis-[Os(CO)2(S2CNMe2)(S3CNMe2)] (2) resulting (formally) from sulfur insertion into an Os-S bond. Heating 1 with further Me4TDS did afford 2, albeit in small amounts and on a timeframe incompatible with its formation under the initial reaction conditions. From the Me4TMS reaction, binuclear [Os2(CO)3(S2CNMe2)2(µ-CNMe2)(µ-SCNMe2)] (3) is a secondary product. It contains dithiocarbamate, thiocarboxamide and amino-carbyne ligands, the last two resulting (formally) from the oxidative addition of a C-S bond in Me4TMS. Both new complexes have been characterised by X-ray crystallography.",

keywords = "Carbonyl, Dithiocarbamate, Osmium, Oxidative-addition, Thiocarboxamide, Trithiocarbamate",

author = "Huda, {Md Nazmul} and Sarker, {Jagodish C.} and Nesterov, {Vladimir N.} and Graeme Hogarth and Kabir, {Shariff E.}",

note = "Publisher Copyright: {\textcopyright} 2024 Elsevier B.V.",

year = "2024",

month = aug,

day = "1",

doi = "10.1016/j.jorganchem.2024.123252",

language = "English",

volume = "1016",

journal = "JOURNAL OF ORGANOMETALLIC CHEMISTRY",

issn = "0022-328X",

publisher = "Elsevier",

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Huda, MN, Sarker, JC, Nesterov, VN, Hogarth, G & Kabir, SE 2024, 'Oxidative-addition of tetramethylthiuram disulfide (Me₄TDS) and monosulfide (Me₄TMS) at a triosmium centre: Generation of dithiocarbamate, trithiocarbamate, thiocarboxamide and amino-carbyne ligands', JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 1016, 123252. https://doi.org/10.1016/j.jorganchem.2024.123252

Oxidative-addition of tetramethylthiuram disulfide (Me₄TDS) and monosulfide (Me₄TMS) at a triosmium centre: Generation of dithiocarbamate, trithiocarbamate, thiocarboxamide and amino-carbyne ligands. / Huda, Md Nazmul; Sarker, Jagodish C.; Nesterov, Vladimir N. et al.
In: JOURNAL OF ORGANOMETALLIC CHEMISTRY, Vol. 1016, 123252, 01.08.2024.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Oxidative-addition of tetramethylthiuram disulfide (Me4TDS) and monosulfide (Me4TMS) at a triosmium centre

T2 - Generation of dithiocarbamate, trithiocarbamate, thiocarboxamide and amino-carbyne ligands

AU - Huda, Md Nazmul

AU - Sarker, Jagodish C.

AU - Nesterov, Vladimir N.

AU - Hogarth, Graeme

AU - Kabir, Shariff E.

PY - 2024/8/1

Y1 - 2024/8/1

N2 - Thermolytic reactions of [Os3(CO)12] with tetramethylthiuram disulfide (Me4TDS) and tetramethylthiuram monosulfide (Me4TMS) are described. While both afford the anticipated bis(dithiocarbamate) complex cis-[Os(CO)2(S2CNMe2)2] (1) as the major product, unexpected secondary products result in both cases. With Me4TDS this is the trithiocarbamate-dithiocarbamate complex cis-[Os(CO)2(S2CNMe2)(S3CNMe2)] (2) resulting (formally) from sulfur insertion into an Os-S bond. Heating 1 with further Me4TDS did afford 2, albeit in small amounts and on a timeframe incompatible with its formation under the initial reaction conditions. From the Me4TMS reaction, binuclear [Os2(CO)3(S2CNMe2)2(µ-CNMe2)(µ-SCNMe2)] (3) is a secondary product. It contains dithiocarbamate, thiocarboxamide and amino-carbyne ligands, the last two resulting (formally) from the oxidative addition of a C-S bond in Me4TMS. Both new complexes have been characterised by X-ray crystallography.

AB - Thermolytic reactions of [Os3(CO)12] with tetramethylthiuram disulfide (Me4TDS) and tetramethylthiuram monosulfide (Me4TMS) are described. While both afford the anticipated bis(dithiocarbamate) complex cis-[Os(CO)2(S2CNMe2)2] (1) as the major product, unexpected secondary products result in both cases. With Me4TDS this is the trithiocarbamate-dithiocarbamate complex cis-[Os(CO)2(S2CNMe2)(S3CNMe2)] (2) resulting (formally) from sulfur insertion into an Os-S bond. Heating 1 with further Me4TDS did afford 2, albeit in small amounts and on a timeframe incompatible with its formation under the initial reaction conditions. From the Me4TMS reaction, binuclear [Os2(CO)3(S2CNMe2)2(µ-CNMe2)(µ-SCNMe2)] (3) is a secondary product. It contains dithiocarbamate, thiocarboxamide and amino-carbyne ligands, the last two resulting (formally) from the oxidative addition of a C-S bond in Me4TMS. Both new complexes have been characterised by X-ray crystallography.

KW - Carbonyl

KW - Dithiocarbamate

KW - Osmium

KW - Oxidative-addition

KW - Thiocarboxamide

KW - Trithiocarbamate

UR - http://www.scopus.com/inward/record.url?scp=85197611437&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2024.123252

DO - 10.1016/j.jorganchem.2024.123252

M3 - Article

AN - SCOPUS:85197611437

SN - 0022-328X

VL - 1016

JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY

JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY

M1 - 123252

ER -

Oxidative-addition of tetramethylthiuram disulfide (Me₄TDS) and monosulfide (Me₄TMS) at a triosmium centre: Generation of dithiocarbamate, trithiocarbamate, thiocarboxamide and amino-carbyne ligands

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