Bis[1,2-bis(dimethylphosphino)ethane]dihydrogenhydridoiron(II) tetraphenylborate as a model for the function of nitrogenases
摘要:
The trihydride complex [FeH3(dmpe)2]+ (dmpe = Me2PCH2CH2PMe2) is best represented as [FeH(H2)(dmpe2]+, with the H-H separation in the H-2 being ca. 0.81 angstrom. The H-2 can be replaced by N2, CO, MeCN, MeNC and C2H4. The dinitrogen complex [FeH(N2)(dmpe)2]+ may be deprotonated to yield the solution-stable, trigonal-bipyramidal species [Fe(N2)(dmpe)2], which can be reprotonated by HCl to yield [FeCl2(dmpe)2], N2, H-2, and NH3. The crystal structures of [FeH(H2)(dmpe)2]BPh4 and [FeH(N2)(dmpe)2]BPh4 have been determined.
Reduction of dinitrogen bound at an iron(0) centre
作者:David A. Hall、G. Jeffery Leigh
DOI:10.1039/dt9960003539
日期:——
It has been confirmed that the deprotonation–reprotonation of dinitrogeniron(II) complexes is a method of producing limited amounts of ammonia. However, the original postulate that such reactions involve an iron(0) dinitrogen complex as the key intermediate may be in error. The species originally identified as such is much more likely to have been a hydrido-complex impurity, and the ammonia-yielding intermediate remains uncharacterised.