We have synthesized several novel palladium allyl and 1,1-dimethylallyl complexes bearing different heteroditopic NHCeS ligands giving rise to a five-membered chelate ring with the metal center.We were able to synthesize some homoleptic bis-carbene allyl derivatives by taking advantage of the hemilability of the thioetheric sulfur. Attempts at preparing mixed bis-carbene complexes bearing two different heteroditopic carbenes (i.e. NHCeS and NHCePy) simultaneously coordinated to the palladium center lead to a carbene transmetalation with the formation of a statistically distributed equilibrium mixture of the two pure homoleptic and of the mixed bis-carbene palladium allyl complexes in solution. In two different cases the rate of the equilibrium reaction was measured and a mechanistic hypothesis provided. Finally, we have determined the solid state structures of a complex bearing only one NHCeS heteroditopic carbene and of the bis-carbene (NHCeS, NHCePy) palladium allyl derivatives.

Synthesis of novel palladium allyl complexes bearing heteroditiopic NHC-S ligands. Kinetic study on the carbene exchange between bis-carbene palladium allyl complexes

CANOVESE, Luciano;VISENTIN, Fabiano;SANTO, Claudio;
2013-01-01

Abstract

We have synthesized several novel palladium allyl and 1,1-dimethylallyl complexes bearing different heteroditopic NHCeS ligands giving rise to a five-membered chelate ring with the metal center.We were able to synthesize some homoleptic bis-carbene allyl derivatives by taking advantage of the hemilability of the thioetheric sulfur. Attempts at preparing mixed bis-carbene complexes bearing two different heteroditopic carbenes (i.e. NHCeS and NHCePy) simultaneously coordinated to the palladium center lead to a carbene transmetalation with the formation of a statistically distributed equilibrium mixture of the two pure homoleptic and of the mixed bis-carbene palladium allyl complexes in solution. In two different cases the rate of the equilibrium reaction was measured and a mechanistic hypothesis provided. Finally, we have determined the solid state structures of a complex bearing only one NHCeS heteroditopic carbene and of the bis-carbene (NHCeS, NHCePy) palladium allyl derivatives.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10278/37448
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