Zr and Hf complexes of bis(phenolate-ether) (“O4”) ligands feature high activity, stereoselectivity and molecular weight capability for propene polymerization at high temperature. Here we report a simplified ligand synthesis and several new examples of O4 ligands. The formation of precatalysts LMR2 (M = Zr, Hf; R = Bn, Me) from LH2 and MR4 was found to be accompanied in some cases by the formation of dimers (μ-L)2[MR2]2, and X-ray structures of two such dimers have been determined. Treatment of LMMe2 with [Ph3C]+[B(C6F5)4]– produces fairly clean cationic species LMMe+ which were studied by 1H NMR. 2D ROESY data, in particular, suggest that for “smaller” O4 ligands the LMMe+ cation reversibly rearranges from the active (fac/fac) form to a presumably inactive fac/mer or mer/mer form; more bulky substituents appear to suppress this rearrangement. Implications for polymerization catalysis are discussed.
Formation and Activation of Zr/Hf Bis(phenolate-ether) Precatalysts / Cuthbert, E. N. T.; Busico, Vincenzo; Herbert, D. E.; Budzelaar, P. H. M.. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - 2019:29(2019), pp. 3396-3410. [10.1002/ejic.201900716]
Formation and Activation of Zr/Hf Bis(phenolate-ether) Precatalysts
Busico Vincenzo;Budzelaar P. H. M.
2019
Abstract
Zr and Hf complexes of bis(phenolate-ether) (“O4”) ligands feature high activity, stereoselectivity and molecular weight capability for propene polymerization at high temperature. Here we report a simplified ligand synthesis and several new examples of O4 ligands. The formation of precatalysts LMR2 (M = Zr, Hf; R = Bn, Me) from LH2 and MR4 was found to be accompanied in some cases by the formation of dimers (μ-L)2[MR2]2, and X-ray structures of two such dimers have been determined. Treatment of LMMe2 with [Ph3C]+[B(C6F5)4]– produces fairly clean cationic species LMMe+ which were studied by 1H NMR. 2D ROESY data, in particular, suggest that for “smaller” O4 ligands the LMMe+ cation reversibly rearranges from the active (fac/fac) form to a presumably inactive fac/mer or mer/mer form; more bulky substituents appear to suppress this rearrangement. Implications for polymerization catalysis are discussed.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.