Synthesis of (HIPTNCH2CH2)3NV Compounds (HIPT = 35-(246-i-Pr3C6H2)2C6H3) and an Evaluation of Vanadium for the Reduction of Dinitrogen to Ammonia

摘要

Green [HIPTN3N]V(THF) ([HIPTN3N]³⁻ = [(HIPTNCH2CH2)3N]³⁻ where HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3) can be prepared in 70–80% yield through addition of H3[HIPTN3N] to VCl3(THF)3 in THF followed by addition of LiN(SiMe3)₂. From [HIPTN₃N]V(THF) the following have been prepared: {[HIPTN₃N]VN₂}K, [HIPTN₃N]V(NH₃), [HIPTN₃N]V=NH, [HIPTN₃N]V=NSiMe₃, [HIPTN₃N]V=O, [HIPTN₃N]V=S, and [HIPTN₃N]V(CO). No ammonia is formed from dinitrogen using {[HIPTN₃N]VN₂}K, [HIPTN₃N]V=NH, or [HIPTN₃N]V(NH₃) as the initial species under conditions that were successful in the analogous [HIPTN₃N]Mo system. X-ray structural studies are reported for [HIPTN₃N]V(THF) and [HIPTN₃N]V(NH₃).