Abstract
The {Fe(NO)2}9 DNIC [PPN][(BPDO)Fe(NO)2] (1) containing oxygen-coordinating ligands was synthesized from reaction of {Fe(NO)2}9 DNIC [PPN][(NO2)2Fe(NO)2] and 1 equvi of [BPDO]2－. The mean Fe-N(O) (1.699(2) Å) and N-O (1.176(2) Å) bond distances of complex 1 fall within the range of {Fe(NO)2}9 DNICs. In comparisons of the Fe-N(O) and N-O bond length of complex 1, [(OPh)2Fe(NO)2].－, [(SEt)2Fe(NO)2]－, and [(SPh)2Fe(NO)2]－ shows that the Fe to NO -back bonding dominates. On the basis of X-ray absorption Fe K-edge spectra, complex 1 prefers {Fe3+(NO－)2}9 electronic structure. In this work, the transformation of complex 1 to the [(PPh3)2Fe(NO)2], [(I)2Fe(NO)2]－ and [(SC7H4SN)2Fe(NO)2]－ was demonstrated via reductive elimination/ oxidative addition pathway. In the presence of O2, complex 1 can act as a nitrating agent that converts DBP to NO2-DBP via formation of a putative iron-peroxynitrite. Finally, the binging affinity of ligands ([NO2]－, [OPh]－, [BPDO]2－) toward the {Fe(NO)2}9 motif fllows the ligand displacement series [NO2]－< [OPh]－~ [BPDO]2－.