Mono- and dinuclear non-heme iron–nitrosyl complexes: Models for key intermediates in bacterial nitric oxide reductases

Berto, Timothy C.; Speelman, Amy L.; Zheng, Sheng; Lehnert, Nicolai

doi:10.1016/j.ccr.2012.05.007

Cited by 159 publications

(258 citation statements)

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“…[10] TheF e À N À Ob ond of 1 is completely linear, compared to the bent FeÀNÀObond of 2 [8] and other {FeNO} 7 complexes. [11] Linearization of the FeÀNÀOm oiety in {FeNO} 6 complexes has been observed previously for low- …”

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confidence: 61%

“…Thec alculated geometric and spectroscopic parameters of 1, 2,a nd 3 are all in excellent agreement with experimental values (Tables S2-S3). In particular, the DFT-calculated and experimental d values show as trong linear correlation (Figure 4), which indicates that DFT is able to properly describe bonding trends within this series.A sr eported previously,t he electronic structure of 2 [8] and other high-spin {FeNO} 7 complexes [11,12] is best described as ah igh-spin Fe III center antiferromagnetically coupled to triplet NO À .T he NO À in these systems acts as aw eak p-acceptor (a-spin), but mainly as as trong p-donor (b-spin) into the iron d xz and d yz orbitals (where the z-axis lies along the Fe À N(O) bond vector), resulting in ah ighly covalent Fe À NO bond. [13] TheD FT calculations reveal an Fe IV ÀNO À electronic structure for 1 consistent with experimental findings.D ue to the higher effective nuclear charge of the iron center in 1 as compared to 2,t he NO À moiety donates additional electron density into the Fe d-orbitals in 1,m aking the Fe À NO bond even more covalent.…”

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Structural and Spectroscopic Characterization of a High‐Spin {FeNO}⁶ Complex with an Iron(IV)−NO⁻ Electronic Structure

et al. 2016

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Although the interaction of low-spin ferric complexes with nitric oxide has been well studied, examples of stable high-spin ferric nitrosyls (sucha st hose that could be expected to form at typical non-heme iron sites in biology) are extremely rare.U sing the TMG 3 tren co-ligand, we have prepared ah igh-spin ferric NO adduct ({FeNO} 6 complex) via electrochemical or chemical oxidation of the corresponding high-spin ferrous NO {FeNO} 7 complex. The {FeNO} 6 compound is characterized by UV/Visible and IR spectroelectrochemistry,M çssbauer and NMR spectroscopy, X-ray crystallography,a nd DFT calculations.T he data show that its electronic structure is best described as ah igh-spin iron(IV) center bound to atriplet NO À ligand with avery covalent iron À NO bond. This finding demonstrates that this high-spin iron nitrosyl compound undergoes iron-centered redoxc hemistry, leading to fundamentally different properties than corresponding low-spin compounds,w hichu ndergo NO-centered redox transformations.

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Structural and Spectroscopic Characterization of a High‐Spin {FeNO}⁶ Complex with an Iron(IV)−NO⁻ Electronic Structure

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“…NO can react with both organic and oxygencentered radicals to yield many highly reactive intermediates. Moreover, NO can also interact with transition-metal ions to make a variety of coordination compounds [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22]. The ν(N-O) stretching energies should provide straightforward insight into the geometric and electronic structure of nitrosyl complexes.…”

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confidence: 99%

Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure

et al. 2016

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The linear nickel-nitrosyl complex [Ni(NO)(L3)] supported by a highly hindered tridentate nitrogen-based ligand, hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate (denoted as L3), was prepared by the reaction of the potassium salt of the ligand with the nickel-nitrosyl precursor [Ni(NO)(Br)(PPh 3 ) 2 ]. The obtained nitrosyl complexes as well as the corresponding chlorido complexes [Ni(NO)(Cl)(PPh 3 ) 2 ] and [Ni(Cl)(L3)] were characterized by X-ray crystallography and different spectroscopic methods including IR/far-IR, UV-Vis, NMR, and multi-edge X-ray absorption spectroscopy at the Ni K-, Ni L-, Cl K-, and P K-edges. For comparative electronic structure analysis we also performed DFT calculations to further elucidate the electronic structure of [Ni(NO)(L3)]. These results provide the nickel oxidation state and the character of the Ni-NO bond. The complex [Ni(NO)(L3)] is best described as [Ni (II) (NO (-) )(L3)], and the spectroscopic results indicate that the phosphane complexes have a similar [Ni (II) (NO (-) )(X)(PPh 3 ) 2 ] ground state.

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“…The exact order of proton and electron additions during their catalytic cycles is not known, nor is the mechanism by which the N-N bond of N 2 O is formed. 5,7 As a result, there is much speculation and debate about how these enzymes operate; [13][14][15] however, a common intermediate to many of these mechanistic proposals is the hyponitrite moiety, [N 2 O 2 ] 2-, 1,7,16 which is formed via coupling of two nitric oxide molecules.…”

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Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Wright

Hayton

2015

Inorg. Chem.

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Herein, we review the preparation and coordination chemistry of the cis and trans isomers of hyponitrite, [N 2 O 2 ] 2-. Hyponitrite is known to bind to metals via a variety of bonding modes. In fact, at least eight different bonding modes have been observed, which is remarkable for such a simple ligand. More importantly, it is apparent that the cis isomer of hyponitrite is more reactive than the trans isomer, as the barrier of N 2 O elimination from cis-hyponitrite is lower than that of trans-hyponitrite. This observation may have important mechanistic implications for both heterogeneous NO x reduction catalysts and NO Reductase. However, our understanding of the hyponitrite ligand has been limited by the lack of a general route to this fragment, and most instances of its formation have been serendipitous.3

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Mono- and dinuclear non-heme iron–nitrosyl complexes: Models for key intermediates in bacterial nitric oxide reductases

Cited by 159 publications

References 99 publications

Structural and Spectroscopic Characterization of a High‐Spin {FeNO}⁶ Complex with an Iron(IV)−NO⁻ Electronic Structure

Structural and Spectroscopic Characterization of a High‐Spin {FeNO}⁶ Complex with an Iron(IV)−NO⁻ Electronic Structure

Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

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Mono- and dinuclear non-heme iron–nitrosyl complexes: Models for key intermediates in bacterial nitric oxide reductases

Cited by 159 publications

References 99 publications

Structural and Spectroscopic Characterization of a High‐Spin {FeNO}6 Complex with an Iron(IV)−NO− Electronic Structure

Structural and Spectroscopic Characterization of a High‐Spin {FeNO}6 Complex with an Iron(IV)−NO− Electronic Structure

Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

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Structural and Spectroscopic Characterization of a High‐Spin {FeNO}⁶ Complex with an Iron(IV)−NO⁻ Electronic Structure

Structural and Spectroscopic Characterization of a High‐Spin {FeNO}⁶ Complex with an Iron(IV)−NO⁻ Electronic Structure