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

An efficient potassium cyanide-promoted synthesis of 2-arylbenzoxazoles from [4.3.0]boron heterobicy...

A flexible access to highly functionalised boronates

Further insight into three center hydrogen bonding. Participation in tautomeric equilibria of hetero...

Synthesis, crystal structures, and quadratic nonlinear optical properties in a series of pushpull bo...

Aroylthioureas: new organic ionophores for heavy-metal ion selective electrodes

Effect of TiO2Al2O3 SolGel Supports on the Superficial Ni and Mo Species in Oxidized and Sulfided Ni...

Synthesis of New Chiral Derivatives of N,N?-Dimethylpropyleneurea (DMPU) and Examination of Their In...

The Structural Chemistry of N-Monolithium Borazines

Highly diastereoselective alkylation, acylation and aldol condensation of cis- and trans-(N-acyloyl)...

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