The reaction of dichlorophenylborane with nitrido complexes of rhenium

BCl2Ph reacts with terminal nitrido ligands of rhenium complexes under formation of a nitrogen bridge between the transition metal and boron. Structural studies on [Re(NBCl2Ph)Cl-2(Ph3P)(2)], [Re(NBCl2Ph)Cl-2(Me2PhP)(3)], [Re(NBCl2Ph)Cl(Me2PhP)(2)(Et(2)dtc)] and [Re(NBCl2Ph)-(Me2PhP)(Et(2)dtc)(2)] (Et(2)dtc(-) = N,N'-diethyldithiocarbamate) demonstrate that the rhenium-nitrogen bond is only slightly lengthened upon the formation of the nitrido bridge whereas a significant decrease of the structural trans influence of the nitrido ligand is observed. [Re(NBCl2Ph)Cl-4(Y)](-) (Y = Cl or solvent) complexes are formed during the reaction of [ReNCl4](-) with BCl2Ph. The rhenium(VI) compounds (d(1)configuration) can easily be detected by EPR spectroscopy. The formation of {Re(NBCl2Ph)} complexes with mixed Cl-/Br- (or NCS-) coordination spheres is evident when the reactions start from [ReNBr4](-) or [ReN(NCS)(5)](2-) which can be derived from the EPR spectra of the reaction mixtures.