A novel nitridotechnetium(V) complex with a tetradentate Schiff base ligand, TcN(bzdbsalpn), was synthesized by the reaction of TcNCl 2(PPh3)2 and N,N′-bis(3,5-di-t-butyl- salicylidene)-2-benzyl-1,3-propanediamine (H2bzdbsalpn). Both the syn- and anti-isomers of TcN(bzdbsalpn) were formed in the solution, but recrystallization of a mixture of syn- and anti-TcN(bzdbsalpn) gave a single crystal only for the syn-isomer. X-ray crystallography showed that the syn-TcN(bzdbsalpn) was in a distorted octahedral structure. The planar tetradentate bzdbsalpn ligand coordinates to the technetium atom in an O-N-N-O equatorial plane and the six-membered Nimine-Nimine chelate ring that includes the propylene group adopts a chair conformation. The nitrido ligand (Tc≡N) is at an apical position and the Tc≡N triple bond length is 1.6 Å. Interestingly, the crystal of syn-TcN(bzdbsalpn) has a nitrido-bridged linear polymeric structure (⋯Tc≡N⋯ Tc≡N⋯) running along the 21 screw axes parallel to the b axis. The intermolecular N⋯Tc distance in the syn-TcN(bzdbsalpn) crystal (∼2.8 Å) is fairly long compared with that reported for Cr(V) and Mn(V) nitrido complexes with analogous Schiff base ligands (∼2.5 Å).
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