Synthesis and Reactivity of Structurally Analogous Phenylimido and Oxo Complexes of Rhenium(V) with N,N‐Dialkyl‐N′‐benzoylthioureas

[ReOCl₃(PPh₃)₂] and [Re(NPh)Br₃(PPh₃)₂] react at room temperature with equivalent amounts of N,N‐dialkyl‐N′‐benzoylthioureas (HR¹R²btu) in CH₂Cl₂ under formation of the rhenium(V) complexes [ReOCl₂(R¹R¹btu)(PPh₃)] and [Re(NPh)Br₂(R¹R²btu)(PPh₃)], respectively. The products are structurally analogous with the oxygen atoms of the benzoylthioureas binding in trans positions to the oxo or phenylimido ligands. Prolonged reaction times result in the reduction of the oxo compound by the released PPh₃ and the formation of rhenium(III) complexes of the composition [ReCl₂(PPh₃)₂(R¹R²btu)], while such a second reaction path is excluded for the phenylimido compound. Phenylimido species with more than one N,N‐dialkyl‐N′‐benzoylthioureato ligand could not be isolated, even when a large excess of HR¹R²btu was used during the reaction.