TY - JOUR
T1 - Preparation and Reactivity of Rhenium-Nitride Complexes Bearing PNP-Type Pincer Ligands toward Nitrogen Fixation
AU - Meng, Fanqiang
AU - Kuriyama, Shogo
AU - Egi, Akihito
AU - Tanaka, Hiromasa
AU - Yoshizawa, Kazunari
AU - Nishibayashi, Yoshiaki
N1 - Funding Information:
The present project is supported by CREST, JST (Grant JPMJCR1541). We acknowledge Grants-in-Aid for Scientific Research (Grants JP20H05671, JP20K21203, and JP22K14675) from JSPS and SPRING GX. F.M. is a recipient of the SPRING GX and the JSPS Predoctoral Fellowships for Young Scientists.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022
Y1 - 2022
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.organomet.2c00312
DO - 10.1021/acs.organomet.2c00312
M3 - Article
AN - SCOPUS:85136304348
JO - Organometallics
JF - Organometallics
SN - 0276-7333
ER -