| Autor: |
Aleksanyan DV; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia. aleksanyan.diana@ineos.ac.ru., Churusova SG; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia. aleksanyan.diana@ineos.ac.ru., Brunova VV; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia. aleksanyan.diana@ineos.ac.ru., Peregudov AS; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia. aleksanyan.diana@ineos.ac.ru., Shakhov AM; N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, ul. Kosygina 4, Moscow, 119991 Russia., Rybalkina EY; Blokhin National Medical Research Center of Oncology of the Ministry of Health of the Russian Federation, Kashirskoe shosse 23, Moscow, 115478 Russia., Klemenkova ZS; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia. aleksanyan.diana@ineos.ac.ru., Kononova EG; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia. aleksanyan.diana@ineos.ac.ru., Denisov GL; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia. aleksanyan.diana@ineos.ac.ru., Kozlov VA; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia. aleksanyan.diana@ineos.ac.ru. |
| Abstrakt: |
The peculiarities of cyclopalladation of a series of non-classical pincer-type ligands based on monothiooxalyl amides bearing ancillary N- or S-donor groups in the amide units have been scrutinized both under conditions of conventional solution-based synthesis and in the absence of a solvent according to a solid-phase methodology including mechanochemical activation. Grinding the functionalized monothiooxamides with PdCl 2 (NCPh) 2 in a mortar or vibration ball mill is shown to serve as an efficient and green alternative to the synthesis of these complex metal-organic systems in solution that can offer such advantages as the absence of any auxiliary and significant rate and yield enhancement, especially for the challenging ligands. The realization of S,N,N- or S,N,S-monoanionic tridentate coordination in the resulting pincer complexes has been confirmed by multinuclear NMR (including 2D NMR) and IR spectroscopy and, in some cases, X-ray diffraction. The course and outcome of the solid-phase reactions have been studied by a combination of different spectroscopic methods as well as SEM/EDS analysis. The preliminary evaluation of cytotoxic activity against several human cancer cell lines has revealed the high potency of some of the cyclopalladated derivatives obtained, rendering further development of solvent-free synthetic routes to this type of complexes very urgent. |
