화학공학소재연구정보센터
Inorganic Chemistry, Vol.49, No.10, 4648-4656, 2010
(dme)MCl3(NNPh2) (dme=dimethoxyethane; M=Nb, Ta): A Versatile Synthon for [Ta=NNPh2] Hydrazido(2-) Complexes
Complexes (dme)TaCl3(NNPh2) (1) and (dme)NbCl3(NNPh2) (2) (dme =1,2-dimethoxyethane) were synthesized from MCl5 and diphenylhydrazine via a Lewis-acid assisted dehydrohalogenation reaction. Monomeric 1 has been characterized by X-ray, IR, UV-vis, H-1 NMR, and C-13 NMR spectroscopy and contains a kappa(1)-bound hydrazido(2-) moiety. Unlike the corresponding imido derivatives, 1 is dark blue because of an LMCT that has been lowered in energy as a result of an N-alpha-N-beta antibonding interaction that raises the highest occupied molecular orbital (HOMO). Reaction of 1 with a variety of neutral, mono- and dianionic ligands generates the corresponding ligated complexes retaining the kappa(1)-bound [Ta-NNPh2] moiety.