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

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 co...

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Published in:Critical studies in media communication 2020-01, Vol.73 (12), p.1158
Main Authors: Gardiner, Michael G, Ho, Curtis C, McGuinness, David S, Liu, Yi Ling
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description 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.
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subjects Catalysis
Catalysts
Cations
Chemical synthesis
Copolymerization
Copolymers
Crystal structure
Decomposition
Ethylene
Ligands
Moisture
Palladium
Room temperature
Solvents
title Air and Moisture Tolerant Synthesis of a Chelated bis(NHC) Methylpalladium(ii) Complex Relevant to Alkyl Migration Processes in Catalysis
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