Reactivity of [ReOCl3(PPh3)2] towards substituted anilines

The reactivity of [ReOCl3(PPh3)2] towards o‐toluidine, m‐toluidine, o‐fluoroaniline, m‐fluoroaniline, p‐bromoaniline, p‐chloroaniline and p‐anisidine was examined and novel rhenium(V) imido complexes [Re(NC6H4R)Cl3(PPh3)2] (R=o‐Me, m‐Me, o‐F, m‐F, p‐Cl, p‐Br, p‐OMe) were obtained. The resulting products were characterized by elemental analysis, electrospray ionization high‐resolution mass spectrometry (ESI‐HRMS), 1H, 13C{1H}, 19F and 31P{1H} NMR, FT‐IR spectroscopy, and X‐ray crystallography. For m‐toluidine, m‐fluroaniline and p‐chloroaniline, the rhenium(V) imido‐amino mononuclear [Re(NC6H4R)Cl3(H2NC6H4R)(PPh3)] (R=m‐F, p‐Cl) complexes and the binuclear [{Re(m‐NC6H4Me)Cl2(m‐H2NC6H4Me)(PPh3)}2O] complex were isolated as side products and characterized by X‐ray crystallography. All six‐coordinate rhenium(V) complexes display distorted octahedral coordination geometry.