RESUMEN
Thermolysis of [H(BPI)Pt(CH3)][OTf] (BPI = 1,3-bis(2-(4-tert-butyl)pyridylimino)isoindole) to release methane and form (BPI)Pt(OTf) is reported. Kinetic, mechanistic, and computational studies point to an unusual anion-assisted pathway that obviates the need for a higher oxidation state intermediate to couple the metal-bound methyl group with the ligand-bound hydrogen. Leveraging this insight, a triflimide derivative of the (BPI)Pt complex was shown to activate benzene, highlighting the role of the counteranion in controlling the activity of these complexes.
Asunto(s)
Platino (Metal) , Aniones , Cinética , Ligandos , Oxidación-Reducción , Platino (Metal)/químicaRESUMEN
A simple and convergent way to synthesize 2-amino-6-bromonaphthalenes involves condensation of free secondary amines with the corresponding 2-naphthol under Bucherer conditions. The amination protocol relies on common Teflon-capped pressure flasks and has been used to modify the tertiary aminonaphthalene core of DANPY, a biocompatible chromophore shown to be safe and effective for staining a variety of cellular targets. Following a Suzuki reaction with pyridine 4-boronic acid, additional diversity is introduced upon N-alkylation to install the pyridinium cation. New DANPY derivatives and intermediates reported herein reflect the modularity of the dye nucleus, including the addition of groups useful for applications in membrane staining and DNA-based biophotonics.