trans‐[TcNCl2(Ph3PNH)2] — Synthesis and Structure

The neutral technetium(V) phosphoraneimine complex TcNCl₂(Ph₂PNH)₂] is formed when (Bu₄N)TcOCl₄] reacts with Me₃SiNPPh₃ in dichloromethane. Distances of 2.078(4) and 2.102(4) Å have been found between Tc and the neutral triphenylphosphoraneimine ligands. The Tc‐N‐P angles are 133.7(3) and 134.8(3)°. The terminal nitrido ligand is formed by decomposition of an additional molecule of Me₃SiNPPh₃. The protons which are used for the protonation of the organic ligands are released during the decomposition of CH₂Cl₂. The same reaction yields the TcNCl₄]^— anion when it is performed in acetonitrile.