Abstract:
The rhenium(V) nitrido compounds cis,mer-[ReNBr2(Me2PhP)3] and mer-[ReNCl(Me2PhP)3 (MetetrazS)] are obtained by ligand substitution starting from cis,mer-[ReNCl2(Me2PhP)3].
The reaction of cis,mer-[ReNCl2(Me2PhP)3] with Me3SiI in dichloromethane results in the formation of trans,mer-[Re(NH3)I2(Me2PhP)3]I3. The unusual protonation of a nitrido ligand is due to the partial decomposition of the solvent.
The nitrido bridged complexes cis,mer-[Re(NBX3)X2(Me2PhP)3] (X = Cl, Br),
(Me2PhPH)[fac-Re(NBBr3)Br3(Me2PhP)2], cis,mer-[Re{NB(Butyl)(SO3Me)2}Cl2-(Me2PhP)3], [Re(NBEt3)(Me2PhP)(Et2dtc)2] and [Re{NB(C6F5)3}Cl(Me2PhP)2(HEt2tcb)] have been isolated from reactions of the rhenium(V) nitrido compounds cis,mer-[ReNX2(Me2PhP)3] (X = Cl, Br, NCS), mer-[ReNCl(Me2PhP)3(MetetrazS)], [ReN-(Me2PhP)(Et2dtc)2] or [ReNCl(Me2PhP)2(HEt2tcb)] with the electrophilic boron compounds BX3 (X = Cl, Br), Fe(CpBBr2)2, BEt3, B(Butyl)(SO3Me)2 or B(C6F5)3.
All products have been studied by crystal structure analysis.