Abstract
Diamagnetic dinitrosyl iron complexes (DNICs) supported by various amido ligands were successfully synthesized through reactions of synthesized low coordinate iron(II) complexes with nitric oxide. The dinitrosyl iron complexes (DNICs), Fe[N(Dipp)(R)]2(NO)2 (Dipp = 2,6- diisopropylphenyl, R = SiMe3, c-C6H11), were characterized as diamagnetic complexes with {FeII(．NO)2}8 configuration. They decompose upon irradiation. From experimental data, the decomposition process can be rationalized as that NO dissociates from DNICs upon irradiation, attacks the bound nitrosyl ligands, and consequently results in NO disproportionation. The reactions of neutral DNICs with various reductants engender the formation of their anionic counterpart DNICs with {FeIII(－NO)2}9 electronic configuration. Characteristic 9-line-splitting around g = 2.016 for the said {FeIII(－NO)2}9 DNICs were observed from room temperature EPR spectroscopy. The observed slow NO disproportionation of anionic DNICs is consistent with the {FeIII(－NO)2}9 configuration in which NO‾ tends reluctantly to dissociate from the Fe centers.) The dinitrosyl manganese complexes (DNMCs) [A]{Mn[N(Dipp) (R)]2(NO)2} (A = Li+(solvent)3 or PPh4+), could also be prepared from the reactions of corresponding Mn(II) amides with NO. An electronic configuration of {MnIII(－NO)2}8 was proposed form experimental data. NO disproportionation reactions were also observed when DNMCs were irradiated.