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(Imido)vanadium(V)‐alkyl, Alkylidene Complexes Exhibiting Unique Reactivities towards Olefins, Phenols, and Benzene via 1,2‐C‐H Bond Activation
Author(s) -
Nomura Kotohiro
Publication year - 2012
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201100298
Subject(s) - chemistry , vanadium , alkyl , reactivity (psychology) , steric effects , medicinal chemistry , pyridine , benzene , ligand (biochemistry) , polymerization , phenols , ethylene , stereochemistry , organic chemistry , catalysis , polymer , pathology , medicine , biochemistry , alternative medicine , receptor
Recent examples for synthesis and reaction chemistry with (imido)vanadium(V)‐alkyl, ‐alkylidene complexes have been briefly summarized. (Arylimido)vanadium(V) dichloride complexes especially containing aryloxo ligands exhibited notable activities for ethylene polymerization, and the reacition pathways for the polymerization/dimerization using (imido)vanadium(V) dichloride complexes containing (2‐anilidomethyl)pyridine ligands can be tuned by modification of the steric bulk in the imido substituents; the adamantylimido analogues exhibited exceptionally high both activity and selectivity in the dimerization. These vanadium(V)‐alkyl complexes showed unique reactivity toward phenols; the reaction proceeds via coordination of phenols to the vanadium. The vanadium(V)‐alkylidene complexes were generated by α‐hydrogen elimination from the dialkyl analogues in the presence of PMe 3 etc.; the subsequent 1,2‐C‐H bond activation of benzene with (arylimido)vanadium(V)‐alkylidene containing 1,3‐(2′,6′‐diiso‐propylphenyl)imidazolin‐2‐iminato (Im DIPP N) ligand took place cleanly.