Carboxylate-Functionalized Mesoionic Carbene Precursors: Decarboxylation, Ruthenium Bonding, and Catalytic Activity in Hydrogen Transfer Reactions
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comunitat-uji-handle2:10234/7053
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http://dx.doi.org/10.1021/acs.organomet.6b00322 |
Metadades
Títol
Carboxylate-Functionalized Mesoionic Carbene Precursors: Decarboxylation, Ruthenium Bonding, and Catalytic Activity in Hydrogen Transfer ReactionsData de publicació
2016Editor
American Chemical SocietyISSN
0276-7333; 1520-6041Tipus de document
info:eu-repo/semantics/articleVersió de l'editorial
http://pubs.acs.org/doi/abs/10.1021/acs.organomet.6b00322Paraules clau / Matèries
Resum
Metalation of a carboxylate-functionalized pyridyl-triazolium salt containing
a N1-bound pyridyl substituent either by direct means with [RuCl2(cymene)]2 or via a
transmetalation procedure involving Ag2O and [RuCl ... [+]
Metalation of a carboxylate-functionalized pyridyl-triazolium salt containing
a N1-bound pyridyl substituent either by direct means with [RuCl2(cymene)]2 or via a
transmetalation procedure involving Ag2O and [RuCl2(cymene)]2 induces rapid
decarboxylation without concomitant metalation. Subsequent metalation of the formed
C4- and C5-unsubstituted triazolium salt is selective and occurs at the C4 position, i.e.
remote from the pyridyl substituent, when the reaction is under kinetic control and at the
C5 position adjacent to the pyridyl group, when the reaction is performed under
thermodynamic control. Preservation of the carboxylate functional group in the complex is
achieved when the corresponding ester-functionalized pyridyl-triazolium salt is metalated
first and then subjected to ester hydrolysis. The formed complex contains a N,C-bidentate
chelating pyridyl-triazolylidene ligand with a pendant carboxylate unit that is not
coordinating to the metal center. These new triazolylidene ruthenium complexes show
modest catalytic activity in alcohol oxidation and better performance in the transfer
hydrogenation of ketones. The data suggest that the presence of a pendant carboxylic acid or ester group is beneficial for
enhancing the activity of the catalyst. [-]
Publicat a
Organometallics 2016, 35, 2256−2266Drets d'accés
© 2016 American Chemical Society
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