Oxidative addition chemistry of bis(4,5-dimethoxybenzo)-1,2,5,6-tetrathiocin with cyclopentadienyl metal carbonyl complexes and the mechanochemical transformation of CpCo(dmobdt) to [CpCo(dmobdt)] <sub>2</sub>
The oxidative addition of tetramethoxy-1,2,5,6-dibenzotetrathiocin (1) to CpCo(CO)<sub>2</sub>, [CpFe(CO)<sub>2</sub>]<sub>2</sub>, [CpMo(CO)<sub>3</sub>]<sub>2</sub> and CpV(CO)<sub>4</sub> in toluene under microwave irradiation (150 °C, 30 min) afforded the complexes CpCo(dmobdt) (2), [Cp<sub>2</sub>Fe<sub>2</sub>(dmobt)(CO)<sub>2</sub>] (3), [Cp<sub>2</sub>Mo<sub>2</sub>(dmobdt)<sub>2</sub>] (4) and [(Cp)<sub>2</sub>V<sub>2</sub>(dmobdt)<sub>2</sub>] (5) [dmobdt = 4,5-dimethoxybenzene-1,2-dithiolate dianion, (MeO)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>S<sub>2</sub><sup>2-</sup>]. Vacuum sublimation of 2 afforded dark blue crystals of the monomeric 16<i>e</i><sup>-</sup> complex, CpCo(dmobdt) (2a), whereas recrystallisation from CH<sub>2</sub>Cl<sub>2</sub> afforded dark blue crystals of the dimeric 18<i>e</i><sup>-</sup> polymorph, [CpCo(dmodt)]<sub>2</sub> (2b). The structures of 2a, 2b, 3, 4 and 5 were determined by X-ray diffraction. DSC studies on 2a and 2b indicated distinct melting points (206 and 216 °C respectively) and VT-PXRD revealed no thermally-induced phase change between 2a and 2b. Conversely, mechanochemical grinding of 2a revealed an irreversible phase transition to 2b.
Authors
- John J. Hayward (ORCID: https://orcid.org/0000-0002-7502-7780)
- Lara K. Watanabe (ORCID: https://orcid.org/0000-0002-0327-5611)
- Jeremy M. Rawson (ORCID: https://orcid.org/0000-0003-0480-5386)
- Daniel J. Cutler (ORCID: https://orcid.org/0000-0002-5051-8743)
- Charles L. B. Macdonald (ORCID: https://orcid.org/0000-0002-0574-1524)
- Nadia T. Stephaniuk (ORCID: https://orcid.org/0000-0002-0749-5355)
- Melanie Pilkington
- Mary El Rayes
- Mike D'Agostino
Institutions
- Dalhousie University (CA)
- King's College London (GB)
- Brock University (CA)
- Universitat de Barcelona (ES)
- University of Windsor (CA)
- University of Guelph (CA)
Publication Details
- Journal
- Dalton Transactions
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5dt01691f
- Primary Topic
- Crystal structures of chemical compounds
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- European Commission
- Natural Sciences and Engineering Research Council of Canada