Structural Characterization of (Arylimido)vanadium(V) Compounds with 2,6‐Difluorophenoxide Ligand

The (arylimido)vanadium(V) compound, [( p ‐MeOC 6 H 4 N)V(O i Pr) 3 ] was demonstrated to undergo ligand exchange reaction with one or two equivalents of 2,6‐difluorophenol, affording the (arylimido)vanadium(V) compounds, [( p ‐MeOC 6 H 4 N)V(O i Pr) 2 (O‐2,6‐F 2 Ph)] and [( p ‐MeOC 6 H 4 N)V(O i Pr)(O‐2,6‐F 2 Ph) 2 ]. Their X‐ray crystallographic analyses elucidated the μ‐isopropoxido‐bridged dimeric structures, wherein each vanadium atom has a trigonal‐bipyramidal arrangement with the imido and bridging isopropoxide ligands in the apical positions. The isopropoxide ligand was selectively employed as a bridging ligand between two central vanadium atoms. On the other hand, the reaction of the (arylimido)vanadium(V) compound, [( p ‐MeOC 6 H 4 N)VCl 3 ] and three equivalents of lithium 2,6‐difluorophenoxide gave the (arylimido)vanadium(V) compound, [( p ‐MeOC 6 H 4 N)V(O‐2,6‐F 2 Ph) 3 ]. In the crystal packing, the thus‐obtained compound showed a distorted trigonal‐bipyramidal environment at the vanadium atoms with the μ‐phenoxido‐bridged dimeric structure, wherein the 2,6‐difluorophenoxide ligand was found to serve as a bridging ligand.