Synthesis of Nitrido(phthalocyaninato)metal(V) Complexes RnPcMN (M = Re,Mo, W) and New Compounds with Nitrido‐Bridges between Rhenium and Elements of the Third Main Group

New tetra‐ and octasubstituted nitrido(phthalocyaninato)metal(V) complexes R_nPcMN (M = Re, Mo, W) were synthesized to obtain soluble nitrido‐bridged phthalocyanines. Phthalocyanines with nitrido bridges between rhenium and boron, aluminium, gallium and indium, respectively, were synthesized from nitrido(tetra‐tert.‐butylphthalocyaninato)rhenium(V) complex, tBu₄PcReN and suitable electrophilic reagents like BCl₃, B(C₆F₅)₃, BPh₃, BEt₃, AlCl₃, GaCl₃, GaBr₃, InCl₃, etc. The nitrido‐bridged compounds prepared show different stabilities depending on the substituents at the boron atom. Additionally, the possibility to increase the nucleophilicity of (C₅H₁₁)₈PcWN by reducing this complex with C₈K was studied. The reaction of the reduced complex with electrophiles, e.g. with tBuMeSiCl, Ph₃SiCl and Me₃GeCl indicates the formation of nitrogen‐bridged complexes.