Abstract
Whereas molybdenum dinitrogen complexes have played a major role as catalytic model systems of nitrogenase, corresponding tungsten complexes were in most cases found to be catalytically inactive. Herein, we present a modified pentadentate tetrapodal (pentaPod) phosphine ligand in which two dimethylphosphine groups of the pentaPodMe (P5Me) ligand have been replaced with phospholanes (Pln). The derived molybdenum complex [Mo(N2)P5Pln] generates 22 and the analogous tungsten complex [W(N2)P5Pln] 7 equivalents of NH3 from N2 in the presence of 180 equiv.s of SmI2(thf)2/H2O, rendering the latter the first tungsten complex chemocatalytically converting N2 to NH3. In contrast, the tungsten complex [W(N2)P5Me] generates ammonia from N2 only in a slightly overstoichiometric fashion. The reasons for these reactivity differences are investigated with the help of spectroscopic and electrochemical methods.
Published Version
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
