Modulation of N^N′-bidentate chelating pyridyl–pyridylidene amide ligands offers mechanistic insights into Pd-catalysed ethylene/methyl acrylate copolymerisation. Issue 18 (14th April 2021)

• Record Type: Journal Article
• Authors: Ó Máille, Gearóid M.; Dall'Anese, Anna; Grossenbacher, Philipp; Montini, Tiziano; Milani, Barbara; Albrecht, Martin
• Is Part Of: Dalton transactions. Volume 50:Issue 18(2021)
• Page Start: 6133
• Page End: 6145
• Publication Date: 2021-04-14
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d1dt00389e
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Careful ligand design led to the detection of either an unprecedented, stable, 4-membered palladacycle or an off-cycle catalyst degradation product. Abstract : The efficient copolymerisation of functionalised olefins with alkenes continues to offer considerable challenges to catalyst design. Based on recent work using palladium complexes containing a dissymmetric N^N′-bidentate pyridyl-PYA ligand (PYA = pyridylidene amide), which showed a high propensity to insert methyl acrylate, we have here modified this catalyst structure by inserting shielding groups either into the pyridyl fragment, or the PYA unit, or both to avoid fast β-hydrogen elimination. While a phenyl substituent at the pyridyl side impedes catalytic activity completely and leads to an off-cycle cyclometallation, the introduction of an ortho -methyl group on the PYA side of the N^N′-ligand was more prolific and doubled the catalytic productivity. Mechanistic investigations with this ligand system indicated the stabilisation of a 4-membered metallacycle intermediate at room temperature, which has previously been postulated and detected only at 173 K, but never observed at ambient temperature so far. This intermediate was characterised by solution NMR spectroscopy and rationalises, in part, the formation of α, β-unsaturated esters under catalytic conditions, thus providing useful principles for optimised catalyst design.