Further studies on the chemistry of tetramethylthiourea-platinum complexes: Evolution of cis-[PtCl{S=C(NMe2)(2)}(PPh3)(2)](+) to the dinuclear monothiocarbamato-sulfido complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+)
Reaction of cis-[PtCl2(PPh3)(2)] with tetramethylthiourea (tmtu) in methanol under various conditions has been re-investigated. In the absence of base, the simple ligand substitution product [PtCl(tmtu)(PPh3)(2)]PF6 can be isolated by addition of excess NH4PF6. The complex was characterised by posit...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Published: |
Elsevier
2015
|
| _version_ | 1796946272677003264 |
|---|---|
| author | Henderson, W. Nicholson, B.K. Fortney-Zirker, R.G. Patel, S. Lane, J.R. Wyllie, M.J. Tiekink, E.R.T. |
| author_facet | Henderson, W. Nicholson, B.K. Fortney-Zirker, R.G. Patel, S. Lane, J.R. Wyllie, M.J. Tiekink, E.R.T. |
| author_sort | Henderson, W. |
| collection | UM |
| description | Reaction of cis-[PtCl2(PPh3)(2)] with tetramethylthiourea (tmtu) in methanol under various conditions has been re-investigated. In the absence of base, the simple ligand substitution product [PtCl(tmtu)(PPh3)(2)]PF6 can be isolated by addition of excess NH4PF6. The complex was characterised by positive-ion ESI mass spectrometry, NMR spectroscopy and an X-ray structure determination. In refluxing methanol with excess Me3N, cis-[PtCl2(PPh3)(2)] reacts with tmtu to give a yellow solution containing the dinuclear monothiocarbamato complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+); the complex was isolated as BPh4- or PF6- salts. The X-ray structure of [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)]BPh4 center dot CHCl3 is described. ESI mass spectrometry has been used to identify various reaction intermediates and by-products in the synthesis of [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+). [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+) acts as a metalloligand, e. g. towards PhHg+, but a pure product was unable to be isolated. DFT calculations suggest the presence of a Hg center dot center dot center dot O=C interaction. (C) 2014 Elsevier B.V. All rights reserved. |
| first_indexed | 2024-03-06T05:29:12Z |
| format | Article |
| id | um.eprints-11628 |
| institution | Universiti Malaya |
| last_indexed | 2024-03-06T05:29:12Z |
| publishDate | 2015 |
| publisher | Elsevier |
| record_format | dspace |
| spelling | um.eprints-116282015-01-02T02:38:21Z http://eprints.um.edu.my/11628/ Further studies on the chemistry of tetramethylthiourea-platinum complexes: Evolution of cis-[PtCl{S=C(NMe2)(2)}(PPh3)(2)](+) to the dinuclear monothiocarbamato-sulfido complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+) Henderson, W. Nicholson, B.K. Fortney-Zirker, R.G. Patel, S. Lane, J.R. Wyllie, M.J. Tiekink, E.R.T. Reaction of cis-[PtCl2(PPh3)(2)] with tetramethylthiourea (tmtu) in methanol under various conditions has been re-investigated. In the absence of base, the simple ligand substitution product [PtCl(tmtu)(PPh3)(2)]PF6 can be isolated by addition of excess NH4PF6. The complex was characterised by positive-ion ESI mass spectrometry, NMR spectroscopy and an X-ray structure determination. In refluxing methanol with excess Me3N, cis-[PtCl2(PPh3)(2)] reacts with tmtu to give a yellow solution containing the dinuclear monothiocarbamato complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+); the complex was isolated as BPh4- or PF6- salts. The X-ray structure of [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)]BPh4 center dot CHCl3 is described. ESI mass spectrometry has been used to identify various reaction intermediates and by-products in the synthesis of [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+). [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+) acts as a metalloligand, e. g. towards PhHg+, but a pure product was unable to be isolated. DFT calculations suggest the presence of a Hg center dot center dot center dot O=C interaction. (C) 2014 Elsevier B.V. All rights reserved. Elsevier 2015 Article PeerReviewed Henderson, W. and Nicholson, B.K. and Fortney-Zirker, R.G. and Patel, S. and Lane, J.R. and Wyllie, M.J. and Tiekink, E.R.T. (2015) Further studies on the chemistry of tetramethylthiourea-platinum complexes: Evolution of cis-[PtCl{S=C(NMe2)(2)}(PPh3)(2)](+) to the dinuclear monothiocarbamato-sulfido complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+). Inorganica Chimica Acta, 425. pp. 154-163. |
| spellingShingle | Henderson, W. Nicholson, B.K. Fortney-Zirker, R.G. Patel, S. Lane, J.R. Wyllie, M.J. Tiekink, E.R.T. Further studies on the chemistry of tetramethylthiourea-platinum complexes: Evolution of cis-[PtCl{S=C(NMe2)(2)}(PPh3)(2)](+) to the dinuclear monothiocarbamato-sulfido complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+) |
| title | Further studies on the chemistry of tetramethylthiourea-platinum complexes: Evolution of cis-[PtCl{S=C(NMe2)(2)}(PPh3)(2)](+) to the dinuclear monothiocarbamato-sulfido complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+) |
| title_full | Further studies on the chemistry of tetramethylthiourea-platinum complexes: Evolution of cis-[PtCl{S=C(NMe2)(2)}(PPh3)(2)](+) to the dinuclear monothiocarbamato-sulfido complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+) |
| title_fullStr | Further studies on the chemistry of tetramethylthiourea-platinum complexes: Evolution of cis-[PtCl{S=C(NMe2)(2)}(PPh3)(2)](+) to the dinuclear monothiocarbamato-sulfido complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+) |
| title_full_unstemmed | Further studies on the chemistry of tetramethylthiourea-platinum complexes: Evolution of cis-[PtCl{S=C(NMe2)(2)}(PPh3)(2)](+) to the dinuclear monothiocarbamato-sulfido complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+) |
| title_short | Further studies on the chemistry of tetramethylthiourea-platinum complexes: Evolution of cis-[PtCl{S=C(NMe2)(2)}(PPh3)(2)](+) to the dinuclear monothiocarbamato-sulfido complex [Pt-2(mu-S){mu-SC(O)NMe2}(PPh3)(4)](+) |
| title_sort | further studies on the chemistry of tetramethylthiourea platinum complexes evolution of cis ptcl s c nme2 2 pph3 2 to the dinuclear monothiocarbamato sulfido complex pt 2 mu s mu sc o nme2 pph3 4 |
| work_keys_str_mv | AT hendersonw furtherstudiesonthechemistryoftetramethylthioureaplatinumcomplexesevolutionofcisptclscnme22pph32tothedinuclearmonothiocarbamatosulfidocomplexpt2musmusconme2pph34 AT nicholsonbk furtherstudiesonthechemistryoftetramethylthioureaplatinumcomplexesevolutionofcisptclscnme22pph32tothedinuclearmonothiocarbamatosulfidocomplexpt2musmusconme2pph34 AT fortneyzirkerrg furtherstudiesonthechemistryoftetramethylthioureaplatinumcomplexesevolutionofcisptclscnme22pph32tothedinuclearmonothiocarbamatosulfidocomplexpt2musmusconme2pph34 AT patels furtherstudiesonthechemistryoftetramethylthioureaplatinumcomplexesevolutionofcisptclscnme22pph32tothedinuclearmonothiocarbamatosulfidocomplexpt2musmusconme2pph34 AT lanejr furtherstudiesonthechemistryoftetramethylthioureaplatinumcomplexesevolutionofcisptclscnme22pph32tothedinuclearmonothiocarbamatosulfidocomplexpt2musmusconme2pph34 AT wylliemj furtherstudiesonthechemistryoftetramethylthioureaplatinumcomplexesevolutionofcisptclscnme22pph32tothedinuclearmonothiocarbamatosulfidocomplexpt2musmusconme2pph34 AT tiekinkert furtherstudiesonthechemistryoftetramethylthioureaplatinumcomplexesevolutionofcisptclscnme22pph32tothedinuclearmonothiocarbamatosulfidocomplexpt2musmusconme2pph34 |