Synthesis, properties, and reactivity of a series of non-heme {FeNO}7/8 complexes: Implications for Fe-nitroxyl coordination

Sanders, Brian C.; Patra, Ashis K.; Harrop, Todd C.

doi:10.1016/j.jinorgbio.2012.08.026

Cited by 27 publications

(22 citation statements)

References 81 publications

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“…Part of the negative charge is further stabilized by the porphyrin π system, due to enhanced π-backbonding between the Fe II and the porphyrin e g (π*) orbitals. Overall similar electronic structures have also been observed for ls-{FeNO} 8 complexes with non-porphyrin ligands. ,, …”

Section: Nitric Oxide In Mammalian Signaling and Immune Defensesupporting

confidence: 75%

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

et al. 2021

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Nitric oxide (NO) is an important signaling molecule that is involved in a wide range of physiological and pathological events in biology. Metal coordination chemistry, especially with iron, is at the heart of many biological transformations involving NO. A series of heme proteins, nitric oxide synthases (NOS), soluble guanylate cyclase (sGC), and nitrophorins, are responsible for the biosynthesis, sensing, and transport of NO. Alternatively, NO can be generated from nitrite by heme- and copper-containing nitrite reductases (NIRs). The NO-bearing small molecules such as nitrosothiols and dinitrosyl iron complexes (DNICs) can serve as an alternative vehicle for NO storage and transport. Once NO is formed, the rich reaction chemistry of NO leads to a wide variety of biological activities including reduction of NO by heme or non-heme iron-containing NO reductases and protein post-translational modifications by DNICs. Much of our understanding of the reactivity of metal sites in biology with NO and the mechanisms of these transformations has come from the elucidation of the geometric and electronic structures and chemical reactivity of synthetic model systems, in synergy with biochemical and biophysical studies on the relevant proteins themselves. This review focuses on recent advancements from studies on proteins and model complexes that not only have improved our understanding of the biological roles of NO but also have provided foundations for biomedical research and for bio-inspired catalyst design in energy science.

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Section: Nitric Oxide In Mammalian Signaling and Immune Defensesupporting

confidence: 75%

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

et al. 2021

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“…Other complexes with this type of ligand framework show similar behavior. 122 Heme systems behave similarly to Wieghardt's [Fe(cyclamac)(NO)] n series. The electronic structure of heme ls-{FeNO} 7 complexes is best described as low-spin Fe(II)− NO • .…”

Section: Discussionmentioning

confidence: 85%

Non-heme High-Spin {FeNO}^6–8 Complexes: One Ligand Platform Can Do It All

et al. 2018

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Heme and non-heme iron-nitrosyl complexes are important intermediates in biology. While there are numerous examples of low-spin heme iron-nitrosyl complexes in different oxidation states, much less is known about high-spin (hs) non-heme iron-nitrosyls in oxidation states other than the formally ferrous NO adducts ({FeNO} in the Enemark-Feltham notation). In this study, we present a complete series of hs-{FeNO} complexes using the TMGtren coligand. Redox transformations from the hs-{FeNO} complex [Fe(TMGtren)(NO)] to its {FeNO} and {FeNO} analogs do not alter the coordination environment of the iron center, allowing for detailed comparisons between these species. Here, we present new MCD, NRVS, XANES/EXAFS, and Mössbauer data, demonstrating that these redox transformations are metal based, which allows us to access hs-Fe(II)-NO, Fe(III)-NO, and Fe(IV)-NO complexes. Vibrational data, analyzed by NCA, directly quantify changes in Fe-NO bonding along this series. Optical data allow for the identification of a "spectator" charge-transfer transition that, together with Mössbauer and XAS data, directly monitors the electronic changes of the Fe center. Using EXAFS, we are also able to provide structural data for all complexes. The magnetic properties of the complexes are further analyzed (from magnetic Mössbauer). The properties of our hs-{FeNO} complexes are then contrasted to corresponding, low-spin iron-nitrosyl complexes where redox transformations are generally NO centered. The hs-{FeNO} complex can further be protonated by weak acids, and the product of this reaction is characterized. Taken together, these results provide unprecedented insight into the properties of biologically relevant non-heme iron-nitrosyl complexes in three relevant oxidation states.

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“…A series of 5C Fe-nitroxyl heme-complexes have been obtained by reducing the corresponding n ¼ 7 compounds with cobaltocene derivatives in nonaqueous medium (154,161). The diamagnetic TFPBr 8 -compound (Table 3) has been isolated and characterized by UV-vis, FTIR, 1 H, 15 N NMR spectroscopies and DFT calculations and is very stable in CH 2 Cl 2 , in the absence of oxygen (155).…”

Section: No 2 -Complexesmentioning

confidence: 99%

Three Redox States of Metallonitrosyls in Aqueous Solution

Bari

Iparraguirre

Slep

2015

NOx Related Chemistry

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Synthesis, properties, and reactivity of a series of non-heme {FeNO}7/8 complexes: Implications for Fe-nitroxyl coordination

Cited by 27 publications

References 81 publications

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

Non-heme High-Spin {FeNO}^6–8 Complexes: One Ligand Platform Can Do It All

Three Redox States of Metallonitrosyls in Aqueous Solution

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Synthesis, properties, and reactivity of a series of non-heme {FeNO}7/8 complexes: Implications for Fe-nitroxyl coordination

Cited by 27 publications

References 81 publications

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

Non-heme High-Spin {FeNO}6–8 Complexes: One Ligand Platform Can Do It All

Three Redox States of Metallonitrosyls in Aqueous Solution

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Non-heme High-Spin {FeNO}^6–8 Complexes: One Ligand Platform Can Do It All