Phenylimido Complexes of Technetium and Rhenium with Maleonitriledithiolate

[Tc(NPh)Cl 3 (PPh 3 ) 2 ] or [Re(NPh)Cl 3 (PPh 3 ) 2 ] react with two equivalents of Na 2 mnt (mnt 2– = 1,2‐dicyanoethene‐1,2‐dithiolate) with formation of anionic complexes of the composition [ M (NPh)(mnt) 2 ] – . The products can be isolated as large red blocks of their AsPh 4 + salts. The complex anions contain square‐pyramidal coordinated metal atoms with the phenylimido ligands in apical positions. The M –N–C bonds are almost linear. A similar phenylimido complex with an additional amino group was synthesized from [Re(NC 6 H 4 ‐4‐NH 2 )Cl 3 (PPh 3 ) 2 ]. The presence of such substituents may allow coupling of the metal complexes to biomolecules such as peptides, proteins, or sugars, provided the M =N bonds are sufficiently stable against hydrolysis.