Chemistry Seminar

Abstract:

The development of polydentate ligands based on ferrocene platform has driven progress in homogeneous catalysis.[1-3]Catalyst longevity and ultra-low catalyst loadings have been used to reach high turnover numbers (TONs > 10,000). These performances were based on original multidentarity effects, which are now used to develop very efficient methods for palladiumcatalysed C–C, C–N and C–O (C–S) cross-couplings, thus direct C–H and O(S)–H functionalizations of demanding substrates including organic chlorides are feasible. The features of robust, air-stable polyphosphine auxiliaries and their performances in recent low loading palladium-catalyzed reactions in direct arylation and etherification (or thioetherification) reactions of heteroaromatics will be detailed.[4,5,6] Mechanisms in oxidative addition and reductive elimination (electroanalysis, kinetics, DFT modeling) have revealed net differences with traditional monophosphine ligands that will be described.[6-12] Finally, the physical properties of constrained polyphosphines related to the intriguing phenomenon of nonbonded spin-spin nuclear J couplings will be discussed.[13]

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