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Reactivity of a platinum-benzamide complex toward acid reagents

AuthorsGimeno-Prat, Antonio; Casas, José M. ; Martín, Antonio ; Baya, Miguel
KeywordsSubstitution reactions
Pincer-chelate ligand interconversion
Pincer ligands
Platinum(II) complexes
Issue Date2016
Citation6th EuCheMS (2016)
AbstractThe use of pincer-type ligands has exponentially increased during the last two decades, as they allow the preparation of more stable complexes whose reactivity can be easily explored. Thus, pincer ligands are widely used for the preparation of new organotransition metal complexes showing multiple applications. The neutral species [Pt(NHC(O)Ph)(P(Ph)2 C 6 H4 CH=NC(O)C6 H4 )] (1) contains an anionic PNC pincer ligand stabilizing the platinum (II) center (fig A). As a consequence of the presence of several nucleophilic centres in 1, this complex shows a rich reactivity toward acid reagents. Thus, the reaction of 1 with HCl in a 1:2 ratio affords the neutral derivative [cis-PtCl2 (P(Ph)2 C6 H4 CH=NC(O)C6 H5 ))] (2), which implies a change in the coordination mode of the ligand from pincer to chelate (fig B). The analogous reaction in a 1:1 ratio produces an equimolecular mixture of unreacted starting material and 2. In contrast, the reactions of 1 with acid reagents with non-coordinating anions (HBF4 , Me3 OBF4 ) in a 1:1 ratio give rise to complexes [Pt(NHC(OH)Ph)(P(Ph)2 C6 H4 CH=NC(O)C6 H4 )][BF4 ] (3) and [Pt(NHC(OCH3 )Ph)(P(Ph)2 C6 H4 CH=NC(O)C6 H4 )][BF4 ] (4), as a result of the selective protonation onto the oxygen atom of the benzamide ligand (fig C). Treatment of 2 with AgClO4 (1:1 molar ratio) in the presence of a mild base affords complex [Pt(P(Ph)2 C6 H4 CH=NC(O)C6 H4 )Cl] (5), therefore providing a facile chelate-pincer interconversion reaction. Complex 5 can subsequently be used to prepare derivatives with labile ligands as [Pt(P(Ph)2 C6 H4 CH=NC(O)C6 H4 ))(NCMe)] (6). In this communication we will discuss these reactions, as well as others involving different acid reagents and some of the complexes presented herein.
DescriptionResumen del trabajo presentado al 6th EuCheMS Chemistry Congress, celebrado en Sevilla (España) del 11 al 15 de septiembre de 2016.
Appears in Collections:(ISQCH) Comunicaciones congresos
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