Synthese und Strukturen von [ReNBr2(Me2PhP)3] und (Me2PhPH)[fac‐Re(NBBr3)Br3(Me2PhP)2]

Syntheses and Structures of ReNBr₂(Me₂PhP)₃] and (Me₂PhPH) fac ‐Re(NBBr₃)Br₃(Me₂PhP)₂] ReNBr₂(Me₂PhP)₃] ( 1 ) has been prepared by the reaction of ReNCl₂(Me₂PhP)₃] with Me₃SiBr in dichloromethane. The bromo complex reacts with BBr₃ under formation of Re(NBBr₃)Br₂(Me₂PhP)₃] ( 2 ) or (Me₂PhPH)fac‐Re(NBBr₃)Br₃(Me₂PhP)₂] ( 3 ) depending on the experimental conditions. The formation of the nitrido bridge leads to a significant decrease of the structural trans influence of the nitrido ligand which is evident by the shortening of the Re‐(trans)Br bond from 2.795(1) Å in ReNBr₂(Me₂PhP)₃] to 2.620(1) Å in fac‐Re(NBBr₃)Br₃(Me₂PhP)₂]^– and 2.598(1) Å in Re(NBBr₃)Br₂(Me₂PhP)₃], respectively.