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CSIRO Publishing, Australian Journal of Chemistry, 12(73), p. 1158, 2020

DOI: 10.1071/ch20194

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Air and Moisture Tolerant Synthesis of a Chelated bis(NHC) Methylpalladium(ii) Complex Relevant to Alkyl Migration Processes in Catalysis

Journal article published in 2020 by Michael G. Gardiner, Curtis C. Ho ORCID, David S. McGuinness, Yi Ling Liu
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

An air- and moisture-tolerant alternate synthetic pathway to the preparation of a cationic chelated bis(NHC) methylpalladium(ii) complex, [{(MesIm)2CH2}Pd(Me)(NCMe)][PF6], is described. The pathway involves the isolation of a bis(NHC) AgI complex, [{(MesIm)2CH2}2Ag2][PF6]2, via metallation of the corresponding diimidazolium salt with Ag2O followed by carbene transfer to [(COD)PdBrMe]. This new method avoids a previously reported unstable intermediate that displayed rapid decomposition at room temperature, attaining the targeted cationic methylpalladium(ii) complex in high yield. CO/ethylene copolymerisation catalysis trials are reported showing solvent dependent catalyst lifetime and copolymer yields. Preliminary ethylene insertion studies are also outlined revealing possible pathways leading towards catalyst deactivation.