The diboration of the N=N double bond of azobenzene was achieved by reaction of the [3]diboraplatinametalloarenophanes derived from ferrocene, [Fe(eta(5)-C5H4)B(NMe2)Pt(PEt3)(2)B(NMe2)( eta(5)-C5H4)], and bis(benzene)chromium, [Cr(eta(6)-C6H5)B(NMe2)Pt (PEt3)(2)B(NMe2)(eta(6)-C6H5)], with an excess of azobenzene in toluene at elevated temperature. The formation of the anticipated ansa-bis(boy)hydrazines was substantiated by the determination of the molecular structure of the chromium derivative by X-ray diffraction. The synthesis of the ansa-bis(boryl)hydrazine derivative of ferrocene could also be accomplished under homogeneous catalysis conditions. Hence, reaction of the well-known [2]boraferrocenophane, [Fe(eta(5)-C5H4)(2)B-2(NMe2)(2)], and azobenzene in the presence of 5 mol % [Pt(PEt3)(3)] afforded the bis-borylated hydrazine derivative in good yields.