Highly Electrophilic, Catalytically Active and Redox‐Responsive Cobaltoceniumyl and Ferrocenyl Triazolylidene Coinage Metal Complexes

Highly Electrophilic, Catalytically Active and Redox‐Responsive Cobaltoceniumyl and Ferrocenyl... A convenient access to a triad of triazoles with ferrocenyl and cobaltoceniumyl substituents is reported. N‐Alkylation, deprotonation and metalation with CuI/AgI/AuI synthons affords the heteroleptic triazolylidene complexes. Due to the combination of neutral, electron‐donating ferrocenyl substituents and cationic, strongly electron‐withdrawing cobaltocenium substituents, the mesoionic carbene (MIC) ligands of these complexes are electronically interesting “push–pull”, “pull–push” and “pull–pull” metalloligands with further switchable redox states based on their fully reversible FeII/FeIII, (ferrocene/ferrocenium) and CoIII/CoII, (cobaltocenium/cobaltocene) redox couples. These are the first examples of metal complexes of (di)cationic NHC ligands based on cobaltoceniumyl substituents. DFT calculated Tolman electronic parameter (TEP) of the new MIC ligands, show these metalloligands to be extremely electron‐poor NHCs with properties unmatched in other carbene chemistry. Utilization of these multimetallic electronically tunable compounds in catalytic oxazoline synthesis and in antitumor studies are presented. Remarkably, 1 mol % of the AuI complex with the dicationic MIC ligand displays full catalytic conversion, without the need for any other additives, in less than 2 hours at ambient temperatures. These results thus firmly establish these new classes of cobaltoceniumyl based (di)cationic MIC ligands as prominent players in several branches of chemistry. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chemistry - A European Journal Wiley

Highly Electrophilic, Catalytically Active and Redox‐Responsive Cobaltoceniumyl and Ferrocenyl Triazolylidene Coinage Metal Complexes

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Publisher
Wiley Subscription Services, Inc., A Wiley Company
Copyright
© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN
0947-6539
eISSN
1521-3765
D.O.I.
10.1002/chem.201705051
Publisher site
See Article on Publisher Site

Abstract

A convenient access to a triad of triazoles with ferrocenyl and cobaltoceniumyl substituents is reported. N‐Alkylation, deprotonation and metalation with CuI/AgI/AuI synthons affords the heteroleptic triazolylidene complexes. Due to the combination of neutral, electron‐donating ferrocenyl substituents and cationic, strongly electron‐withdrawing cobaltocenium substituents, the mesoionic carbene (MIC) ligands of these complexes are electronically interesting “push–pull”, “pull–push” and “pull–pull” metalloligands with further switchable redox states based on their fully reversible FeII/FeIII, (ferrocene/ferrocenium) and CoIII/CoII, (cobaltocenium/cobaltocene) redox couples. These are the first examples of metal complexes of (di)cationic NHC ligands based on cobaltoceniumyl substituents. DFT calculated Tolman electronic parameter (TEP) of the new MIC ligands, show these metalloligands to be extremely electron‐poor NHCs with properties unmatched in other carbene chemistry. Utilization of these multimetallic electronically tunable compounds in catalytic oxazoline synthesis and in antitumor studies are presented. Remarkably, 1 mol % of the AuI complex with the dicationic MIC ligand displays full catalytic conversion, without the need for any other additives, in less than 2 hours at ambient temperatures. These results thus firmly establish these new classes of cobaltoceniumyl based (di)cationic MIC ligands as prominent players in several branches of chemistry.

Journal

Chemistry - A European JournalWiley

Published: Jan 12, 2018

Keywords: ; ; ; ;

References

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