title: Selective Catalytic Reduction of N2to N2H4by a Simple Fe Complex.
abstract: The catalytic fixation of N2by molecular Fe compounds is a rapidly developing field, yet thus far few complexes can effect this transformation, and none are selective for N2H4production. Herein we report that the simple Fe(0) complex Fe(Et2PCH2CH2PEt2)2(N2) (1) is an efficient catalyst for the selective conversion of N2(>25 molecules N2fixed) into N2H4, attendant with the production of ca. one molecule of NH3. Notably, the reductant (CoCp*2) and acid (Ph2NH2OTf) used are considerably weaker than conventional chemical H+and e-sources used in previous demonstrations of N2turnover by synthetic Fe compounds. These results show that the direct catalytic conversion of N2to the hydrazine oxidation state on molecular Fe complexes is viable and that the mechanism of NH3formation by such systems may proceed via Fe-N2H4intermediates.
authors.affiliation: Department of Chemistry, Imperial College London , Imperial College Road, South Kensington, London SW7 2AZ, United Kingdom.
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Hill
authors.affiliation: Department of Chemistry, Imperial College London , Imperial College Road, South Kensington, London SW7 2AZ, United Kingdom.
authors.forename: Laurence R
authors.initials: LR
authors.lastname: Doyle
authors.affiliation: Department of Chemistry, Imperial College London , Imperial College Road, South Kensington, London SW7 2AZ, United Kingdom.
authors.forename: Andrew D
authors.initials: AD
authors.lastname: Crawford
authors.affiliation: Centre for Advanced Electron Spin Resonance, Inorganic Chemistry Laboratory, University of Oxford , South Parks Road, Oxford OX1 3QR, United Kingdom.
authors.forename: William K
authors.initials: WK
authors.lastname: Myers
authors.affiliation: Department of Chemistry, Imperial College London , Imperial College Road, South Kensington, London SW7 2AZ, United Kingdom.
authors.forename: Andrew E
authors.initials: AE
authors.lastname: Ashley