Synthesis of [(HIPTNCH2CH2)3N]V compounds (HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3) and an evaluation of vanadium for the reduction of dinitrogen to ammonia.
Green [HIPTN3N]V(THF) ([HIPTN3N]3- = [(HIPTNCH2CH2)3N]3-, where HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3) can be prepared in a 70-80% yield via the addition of H3[HIPTN3N] to VCl3(THF)3 in THF, followed by the 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).
Smythe
Nathan C
NC
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Schrock
Richard R
RR
Müller
Peter
P
Weare
Walter W
WW
D000641:Ammonia / Q000737:chemistry*; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D009584:Nitrogen / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D013055:Spectrophotometry, Infrared; D013696:Temperature; D013730:Terphenyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D014639:Vanadium / Q000737:chemistry*
D009942:Organometallic Compounds; D013730:Terphenyl Compounds; D014639:Vanadium; D000641:Ammonia; D009584:Nitrogen