Unique syndio-selectivity in CO/styrene copolymerization reaction catalyzed by palladium complexes with 2-(2'-oxazolinyl)-1,10-phenanthrolines

Dalton Transactions : an International Journal of Inorganic Chemistry
Angelo MeduriBarbara Milani

Abstract

The reaction of the neutral Pd complex [Pd(CH(3))Cl(cod)] with the potentially terdentate 2-oxazolinyl phenanthroline ligands 1-3 affords the corresponding cationic dinuclear Pd-complexes 1a-3a, which can be isolated in the solid state in good yields. By treatment with AgPF(6) the complexes 1a-3a were converted into the corresponding hexafluorophosphate derivatives 1b-3b, where both the ligand units feature a terdentate coordination around the two Pd-centres with the phenanthroline fragment of each unit displaying a chelate coordination to one Pd-centre, while the corresponding oxazolinyl pendant acts as a bridging ligand towards the second Pd-centre. The persistence of this dimeric structure of 1b-3b in CD(2)Cl(2) solution was confirmed by (15)N-NMR experiments at natural abundance, which clearly show the binding to the metal of all of the nitrogen donors, as well as the overall C(2) symmetry of the compound. In consequence of the different strengths of the relevant ion-pair, the dimeric structure of the complex undergoes partial fragmentation in the case of the chloride derivatives 1a-3a, as evidenced from the (15)N-NMR spectra. Complexes 1b-3b are active catalysts in styrene alternate carbonylation, where, under very mild co...Continue Reading

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Citations

Mar 19, 2016·Chemistry : a European Journal·Jesús CamposErnesto Carmona
Sep 9, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·V RosarB Milani

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