Uncatalyzed hydroamination of electrophilic organometallic alkynes: fundamental, theoretical, and applied aspects.

摘要: Simple reactions of the most used functional groups allowing two molecular fragments to link under mild, sustainable conditions are among crucial tools chemistry with multiple applications in materials science, nanomedicine, and organic synthesis as already exemplified by peptide "click" chemistry. We concerned redox organometallic compounds that can potentially be biosensors catalysts report an uncatalyzed reaction between primary secondary amines electrophilic alkynes is free side products fully "green". A strategy first proposed synthesize alkynyl precursors upon addition aromatic ligands cationic complexes followed endo hydride abstraction. Electrophilic alkynylated cyclopentadienyl or arene Fe, Ru, Co subsequently react yield trans-enamines conjugated group. The difference reactivities various rationalized from two-step mechanism was elucidated through DFT calculations. Applications illustrated facile ethynylcobalticenium hexafluorophosphate aminated silica nanoparticles. Spectroscopic, nonlinear-optical electrochemical data, well TDDFT calculations, indicate a strong push-pull conjugation these cobalticenium- Fe- Ru-arene-enamine due planarity near-planarity trans-enamine involving fulvalene iminium cyclohexadienylidene mesomeric forms.