Through nitrosylation of [Fe–S] proteins, or the
chelatable
iron pool, a dinitrosyl iron unit (DNIU) [Fe(NO)2] embedded
in the form of low-molecular-weight/protein-bound dinitrosyl iron
complexes (DNICs) was discovered as a metallocofactor assembled under
inflammatory conditions with elevated levels of nitric oxide (NO)
and superoxide (O2
–). In an attempt to
gain biomimetic insights into the unexplored transformations of the
DNIU under inflammation, we investigated the reactivity toward O2
– by a series of DNICs [(NO)2Fe(μ-MePyr)2Fe(NO)2] (1) and [(NO)2Fe(μ-SEt)2Fe(NO)2] (3). During the superoxide-induced conversion
of DNIC 1 into DNIC [(K-18-crown-6-ether)2(NO2)][Fe(μ-MePyr)4(μ-O)2(Fe(NO)2)4] (2-K-crown)
and a [Fe3+(MePyr)
x
(NO2)
y
(O)
z
]
n
adduct, stoichiometric NO monooxygenation
yielding NO2
– occurs without the transient
formation of peroxynitrite-derived •OH/•NO2 species. To study the isoelectronic reaction of O2(g) and one-electron-reduced DNIC 1, a DNIC featuring
an electronically localized {Fe(NO)2}9-{Fe(NO)2}10 electronic structure, [K-18-crown-6-ether][(NO)2Fe(μ-MePyr)2Fe(NO)2] (1-red), was successfully synthesized and characterized.
Oxygenation of DNIC 1-red leads to the similar assembly
of DNIC 2-K-crown, of which the electronic structure
is best described as paramagnetic with weak antiferromagnetic coupling
among the four S = 1/2 {FeIII(NO
–
)2}9 units and S = 5/2 Fe3+ center. In contrast to DNICs 1 and 1-red, DNICs 3 and [K-18-crown-6-ether][(NO)2Fe(μ-SEt)2Fe(NO)2] (3-red) display a reversible equilibrium of “3 + O2
– ⇋ 3-red + O2(g)”, which is ascribed to the covalent [Fe(μ-SEt)2Fe] core and redox-active [Fe(NO)2] unit. Based
on this study, the supporting/bridging ligands in dinuclear DNIC 1/3 (or 1-red/3-red) control the selective monooxygenation of NO and redox interconversion
between O2
– and O2 during
reaction with O2
– (or O2).