A series of mononuclear rhenium(V)-nitride complexes bearing substituted pyridine-based PNP-type pincer ligands are synthesized. The substituent in the PNP-type pincer ligand does not significantly improve the catalytic activity for ammonia formation, while the introduction of a methoxy group increases the catalytic activity for the silylamine formation. Stoichiometric studies reveal that a rhenium(V)-nitride complex bearing a nonsubstituted PNP-type pincer ligand is transformed into a dearomatized rhenium(V)-nitride dimer under reductive conditions, while the dearomatized rhenium(V)-nitride dimer exhibits catalytic activity for the nitrogen fixation reactions. However, a rhenium(V)-nitride complex bearing a methyl-substituted PNP-type pincer ligand shows different reactivity by reduction, where deprotonation of the methylene group of the PNP-type pincer ligand is observed.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry