Producción Científica Profesorado

Bridged N?Heterocyclic/Mesoionic (NHC/MIC) Heterodicarbenes as Ligands for Transition Metal Complexes



Alvarez Hernandez, Alejandro

2017

Bridged N?Heterocyclic/Mesoionic (NHC/MIC) Heterodicarbenes as Ligands for Transition Metal Complexes. Daniel Mendoza-Espinosa, Alejandro Alvarez-Herna?ndez, Deyanira Angeles-Beltra?n, Guillermo E. Negro?n-Silva, Oscar R. Sua?rez-Castillo, and Jose? M. Va?squez-Pe?rez Inorg. Chem., 2017, 56, 2092?2099


Abstract


Following a copper catalyzed alkyne azide cycloaddition (CuAAC) and N-alkylation protocols, we report the preparation of a hybrid N-heterocyclic/mesoionic [NHC(H+)-MIC(H+)][2I]2? salt (1) in high yields. The treatment of salt 1 with Cu2O and KI yields a second hybrid NHC/MIC proligand featuring a tetraiodocuprate anion [NHC(H+)-MIC(H+)][Cu2I4]2? (2). Through selective deprotonation and metalation, both salts 1 and 2 can generate either the chelate heterodicarbene complexes (3) with the rare [NHC(M)MIC]+[MX2]? general formula (M = PdII, RhI) or NHC-anchored/pendent triazolium species (4) [NHC(M)-MIC(H+)]. If the triazolium moiety of type 4 complexes is deprotonated with KHMDS in the presence of a second metal center, a series of heterobimetallic complexes of the type [NHC(M)-MIC(M?)] (5) are achieved. Interestingly, the reaction of salt 2 with KHMDS yields the bimetallic copper heterodicarbene (6) which can be a useful transfer reagent for the preparation of type 3 complexes. A variety of synthetic routes for the preparation of complexes 3?5 and their full characterization in solution and in the solid state will be discussed.



Producto de Investigación




Artículos relacionados

Diastereoselective alkylation of chiral glycinate derivatives containing the ?-phenylethyl group.

Et3, and efficient Mediator for Xanthate Transfer Based Radical Processes.

Structural studies of spiroarsoranes derived from 2-aminophenols

Preparation of N-aryl-substituted spiro-?-lactams via Staudinger cycloaddition

A flexible access to highly functionalised boronates

New boronates prepared from 2,4-pentanedione derived ligands of the NO2 and N2O2 type comparison to...

O-benzyl-N-(2-furoyl)thiocarbamate

3-Benzoyl-2-isopropyl-4-alkyloxazolidin-5-ones as Efficient and Inexpensive Sources of Enantiopure ?...

Structure-Activity Relationships for Inhibition of Cysteine Protease Activity and Development of Pla...

Enantioselective synthesis of ?-amino acids. Part 11: Diastereoselective alkylation of chiral deriva...