Coordination of a complete series of N2 reduction intermediates (N2H2, N2H4, and NH3) to an iron phosphine scaffold.
The series of dinitrogen reduction intermediates (N(2)H(2), N(2)H(4), and NH(3)) coordinated to the Fe(DMeOPrPE)(2)H(+)(DMeOPrPE = 1,2-[bis(dimethoxypropyl)phosphino]ethane) scaffold has been synthesized or generated. The synthesis of trans-[Fe(DMeOPrPE)(2)(NH(3))H][BPh(4)] and generation of trans-[Fe(DMeOPrPE)(2)(N(2)H(4))H][BPh(4)] were achieved by substitu tion of the dinitrogen ligand on trans-[Fe(DMeOPrPE)(2)(N(2))H][BPh(4)]. The trans-[Fe(DMeOPrPE)(2)(N(2)H(2))H](+) complex and its deprotonated conjugate base, trans-Fe(DMeOPrPE)(2)(N(2)H)H, were observed by (31)P and (1)H NMR from decomposition of trans-[Fe(DMeOPrPE)(2)(N(2)H(4))H](+) in the presence of excess hydrazine. Attempts to chemically oxidize trans-[Fe(DMeOPrPE)(2)(N(2)H(4))H](+) to trans-[Fe(DMeOPrPE)(2)(N(2)H(2))H][BPh(4)] with a variety of oxidizing agents yielded only decomposition products consistent with the intermediate formation of trans-[Fe(DMeOPrPE)(2)(N(2)H(2))H](+) prior to decomposition.
Department of Chemistry, University of Oregon, Eugene, Oregon 97403, USA.
Justin L
JL
Crossland
Chantal G
CG
Balesdent
David R
DR
Tyler
D007094:Imides / Q000138:chemical synthesis / Q000737:chemistry; D058085:Iron Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D017672:Nitrogen Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010720:Phosphines / Q000138:chemical synthesis / Q000737:chemistry*
D007094:Imides; D058085:Iron Compounds; D017672:Nitrogen Compounds; D010720:Phosphines; C044646:phosphine; C038867:diazene