title: Nitrogen fixation revisited on iron(0) dinitrogen phosphine complexes.
abstract: A reinvestigation of the treatment of [Fe(N2)(PP)2] (PP = depe, dmpe) with acid revealed no ammonium formation. Instead, rapid protonation at the metal center to give hydride complexes was observed. Treatment of [Fe(N2)(dmpe)2] with methylating agents such as methyl triflate or methyl tosylate resulted in methylation of the metal center to afford [FeMe(N2)(dmpe)2](+). Treatment of [Fe(N2)(dmpe)2] with trimethylsilyl triflate, however, resulted in reaction at dinitrogen affording NH4(+) on subsequent treatment with acid. The side-on bound hydrazine complex [Fe(N2H4)(dmpe)2](2+) and bis(ammonia) complex [Fe(NH3)2(dmpe)2](2+) were identified by (15)N NMR spectroscopy as other species formed in the reaction mixture.
authors.affiliation: †School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia.
authors.forename: Leslie D
authors.initials: LD
authors.lastname: Field
authors.affiliation: ‡Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520, United States.
authors.forename: Nilay
authors.initials: N
authors.lastname: Hazari
authors.affiliation: †School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia.
authors.forename: Hsiu L
authors.initials: HL
authors.lastname: Li
mesh_terms: D000641:Ammonia / Q000737:chemistry; D001557:Benzenesulfonates / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry*; D006834:Hydrazines / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008698:Mesylates / Q000737:chemistry; D009584:Nitrogen / Q000737:chemistry*; D009586:Nitrogen Fixation; D010720:Phosphines / Q000737:chemistry*; D011522:Protons; D014297:Trimethylsilyl Compounds / Q000737:chemistry
chemical_list: D001557:Benzenesulfonates; D056831:Coordination Complexes; D006834:Hydrazines; D008698:Mesylates; D010720:Phosphines; D011522:Protons; D014297:Trimethylsilyl Compounds; C029424:hydrazine; C078465:methyl triflate; C506825:methyl tosylate; D000641:Ammonia; D007501:Iron; D009584:Nitrogen