Well‐defined Nickel P3C Complexes as Hydrogenation Catalysts of N‐Heteroarenes Under Mild Conditions. Issue 11 (14th April 2022)

• Record Type: Journal Article
• Authors: Michaliszyn, Klaudia; Smirnova, Ekaterina S.; Bucci, Alberto; Martin‐Diaconescu, Vlad; Lloret Fillol, Julio
• Is Part Of: ChemCatChem. Volume 14:Issue 11(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-04-14
• Subjects: frustrated Lewis pairs -- H2 activation -- hydrogenation -- Ni complexes -- mechanistic study; Catalysis -- Periodicals; 541.39505
• DOI: 10.1002/cctc.202200039
• Languages: English
• ISSNs: 1867-3880

Abstract

Abstract: The reactivity of metal complexes can be primarily controlled by their coordinating ligands. Electronic effects and geometric restrictions imposed by ligands, prototypically modify their reactivity, but are not always straightforward accessible. In the course of the study, we explored new C3 ‐symmetric organometallic nickel (II) complexes ((P3 C )Ni )) with the particularity of having a metalated apical carbon trans to a labile coordination site readily available as a catalytic site. The synthetic methodology allowed to tune the electronic properties by introducing substituents on the phosphines. We studied the nature of the C−Ni bond by X‐ray absorption spectroscopy (XAS) and DFT and applied them to the catalytic hydrogenation of quinolines with a good chemical scope and group tolerance. 1 H‐NMR monitoring, isotopic labelling, and computational studies are consistent with a heterolytic activation of the dihydrogen molecule after forming a σ‐H2 adduct trans to the metalated carbon. Abstract : Herein it is reported a straightforward path to the rare and difficult access of metal complexes with P3 C ligands type and study their capacity as hydrogenation of quinolines.