Air- and water-stable phenyl complexes with nitridotechnetium(V) cores can be prepared by straightforward procedures. [TcNPh2(PPh3)(2)] is formed by the reaction of [TcNCl2(PPh3)(2)] with PhLi. The analogous N-heterocyclic carbene (NHC) compound [TcNPh2(HLPh)(2)], where HLPh is 1,3,4-triphenyl-1,2,4-triazol-S-ylidene, is available from (NBu4)[TcNCl4] and HLPh or its methoxo-protected form. The latter compound allows the comparison of different Tc-C bonds within one compound. Surprisingly, the Tc chemistry with such NHCsdoes not resemble that of corresponding Re complexes, where CH activation and orthometalation dominate.