title: Solid-phase cyclopalladation in S,C,S'-pincer systems: rising alternative for synthesis in solution.
abstract: In pursuit of a new and simple approach to complex organometallic systems, the possibility of formation of a palladium-carbon bond in the solid state via direct cyclopalladation has been studied toward several S,C,S'-pincer ligands with thione sulfur donors of different nature. It is found that mixtures of the ligand and PdCl2(NCPh)2 obtained by the manual grinding of reactants in a mortar efficiently undergo solid-phase cyclometalation upon heating in open test tubes without the addition of a solvent to afford the desired pincer-type products in high yields. In the case of the most active bis(thiocarbamoyl) ligand, solid-phase cyclopalladation proceeds even at room temperature. For the challenging bis(thiophosphoryl) derivative, the preformed non-metallated complexes can be successfully used as a starting material to essentially enhance the yield of the desired pincer complex compared to the conventional synthesis in solution. The solid-phase transformation is followed by IR spectroscopy and SEM analysis. The results obtained show that the suggested solid-phase methodology can serve as a powerful alternative to conventional synthesis of pincer complexes in solution.
authors.affiliation: A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991, Russia. aleksanyan.diana@ineos.ac.ru.
authors.forename: Diana V
authors.initials: DV
authors.lastname: Aleksanyan
authors.forename: Zinaida S
authors.initials: ZS
authors.lastname: Klemenkova
authors.forename: Andrei A
authors.initials: AA
authors.lastname: Vasil'ev
authors.forename: Arkadii Ya
authors.initials: AY
authors.lastname: Gorenberg
authors.forename: Yulia V
authors.initials: YV
authors.lastname: Nelyubina
authors.forename: Vladimir A
authors.initials: VA
authors.lastname: Kozlov
mesh_terms: D018360:Crystallography, X-Ray; D010165:Palladium / Q000737:chemistry*; D060327:Solid-Phase Synthesis Techniques / Q000379:methods*; D012996:Solutions / Q000138:chemical synthesis*
chemical_list: D012996:Solutions; D010165:Palladium; C008756:palladium chloride