Reactivity and Structure of Complexes of Small Molecules: Nitric Oxide

Harland, Jill B.; Manickas, Elizabeth C.; Hunt, Andrew P.; Lehnert, Nicolai

doi:10.1016/b978-0-08-102688-5.00111-2

Cited by 8 publications

(29 citation statements)

References 638 publications

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Section: The Nitrogen Cyclementioning

confidence: 99%

“…Finally, non-heme iron sites are also used as sensors in biology, and they are potentially involved in the biosynthesis of N-nitroso and related natural products (see below as well). Besides the interest in these species originating from their biological relevance, hs-{FeNO} 7 complexes have also been a rich area of study for coordination chemists due to their interesting electronic properties (see ref for a recent review).…”

Section: Non-heme Iron Centers and Nomentioning

confidence: 99%

“…It is for this reason that these complexes have very similar electronic properties and that their reactivities are similar as well, due to the presence of an electrophilic NO + ligand. This example highlights a key strength of the Enemark–Feltham notation, allowing us to categorize transition metal–NO complexes by their number of valence electrons plus the spin state of the metal center, with the general presumption that complexes with the same Enemark–Feltham index n and spin state have similar geometric and electronic structures and reactivities. , …”

Section: Introductionmentioning

confidence: 97%

“…NO is a molecule with a long history in coordination chemistry research, due to its very interesting properties as a ligand, and its reactivity with transition metals has been studied for more than 150 years. , A particular fascination of this chemistry originates from the fact that NO is a “non-innocent” (i.e., redox-active) ligand , that can change oxidation state when binding to a transition-metal center, with common oxidation states being NO + , NO • , and NO – . In addition, the bonds between NO and transition metals are often times very covalent, which provides further challenges in arriving at sound descriptions of the electronic structures of these complexes.…”

Section: Introductionmentioning

confidence: 99%

“…Also, the exact sequence of nitrite binding versus electron/proton transfer to the Type 2 copper site is controversial. − In 2004, Murphy and coworkers reported the crystal structure of CuNIR with NO bound in an unusual, side-on fashion . This result gathered much attention in the community and inspired more work on CuNIRs, − and also enticed inorganic chemists to study additional {CuNO} 10 and {CuNO} 11 model complexes. , The discovery of domain extended CuNIRs provided further stimulation for this field. − Heme cd 1 nitrite reductases are generally homodimers, with an N-terminal heme c domain and a C-terminal heme d 1 domain in each monomeric subunit (see Section ). Heme d 1 is unique to denitrifiers and has a unique structure where the porphyrin ring is oxidized and decorated with two carbonyl groups (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

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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: The Nitrogen Cyclementioning

confidence: 99%

Section: Non-heme Iron Centers and Nomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

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A New Member of the Growing Family of Interconvertible {RuNO}^6,7,8 Species. Redox and Acid‐Base Characterization of [Ru((CH₂py)₂Me[9]aneN₃)(NO)]ⁿ⁺

et al. 2021

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Dedicated to Prof. José A. Olabe on the occasion of his 80th birthdayThe preparation and characterization of a new ruthenium nitrosyl based on the pentadentate ligand (CH 2 py) 2 Me[9]aneN 3 (1-methyl-4,7-bis(pyridin-2-ylmethyl)-1,4,7-triazacyclononane) is reported. The octahedral species contains a {RuNO} 6 fragment and can be isolated in the solid state as a PF 6 À salt. In acetonitrile, this platform allows exploring the reduction processes in 1-electron steps from {RuNO} 6 to {RuNO} 8 , with associated E°values of 0.421 V and À 0.628 V (vs. Ag/AgCl, 3 M NaCl), respectively. The {RuNO} 7 species is paramagnetic, its EPR spectrum in vitrified acetonitrile at 90 K is consistent with an S = 1 = 2 center with g = (2.0095, 1.9992, 1.8785) coupled to a 14 N nucleus, with A = (6.9, 30.24, 1.85) × 10 À 4 cm À 1 . In acidified aqueous solution, the first reduction process at 0.101 V leads to the formation of {RuNO} 7 , as in aprotic medium (acetonitrile). However, the incorporation of a second electron is coupled to a protonation process of the nitroxyl group, generating a coordinated azanone (HNO) compound with pK a (HNO) = 11.0. Spectroscopic information obtained via spectroelectrochemistry and electronic structure calculations assist in the rationalization of results. Overall, this new compound enhances the library of nitrosylated Ru species with combined redox, acid-base, and spectroscopic characterization in water and confirms experimental correlations found in related species.

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Stable Bimetallic Fe^II/{Fe(NO)₂}⁹ Moiety Derived from Reductive Transformations of a Diferrous-dinitrosyl Species

et al. 2022

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A dimeric dithiolate-bridged species, [Fe(NO)(PS2)]2 (1) containing two {FeNO}7 units, can be isolated by treating [Fe(CO)2(NO)2] with PS2H2 (PS2H2 = bis(2-dimercaptophenyl)phenylphosphine). Crystallographic studies reveal the syn-configuration of NO units and the bridging thiolates in the butterfly shape of the 2Fe2S core. Addition of PPh3 to the solution of dinuclear 1 leads to the formation of mononuclear {FeNO}7 [Fe(NO)(PS2)(PPh3)] (2) that shows electrochemical responses similar to those of 1. One-electron reduction of 1 with Cp*2Co or KC8 results in the isolation of thiolate-bridged bimetallic DNIC, [(PS2)Fe(μ-PS2)Fe(NO)2]− ([3]−), confirmed by several spectroscopies including single-crystal X-ray diffraction studies. The bimetallic DNIC [3]− is a rare example obtained from the one-electron reduction of a dinuclear Fe-NO {FeNO}7 model complex. With the assistance of redox behaviors of 2, electrochemical studies imply that the reduction of 1 leads to the formation of a mononuclear {FeNO}8 [Fe(NO)(PS2)(THF)]− intermediate, which involves disproportionation or NO– transfer to yield [3]−. Based on IR data and magnetic properties, the electronic structure of [3]− can be described as a FeII/{Fe(NO)2}9 state. Isolation of the {Fe(NO)2}9 moiety coordinated by the Fe ancillary complex lends strong support to the NO scrambling behavior in the effectiveness of the activity of flavodiiron nitric oxide reductases (FNORs).

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Reactivity and Structure of Complexes of Small Molecules: Nitric Oxide

Cited by 8 publications

References 638 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

A New Member of the Growing Family of Interconvertible {RuNO}^6,7,8 Species. Redox and Acid‐Base Characterization of [Ru((CH₂py)₂Me[9]aneN₃)(NO)]ⁿ⁺

Stable Bimetallic Fe^II/{Fe(NO)₂}⁹ Moiety Derived from Reductive Transformations of a Diferrous-dinitrosyl Species

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Reactivity and Structure of Complexes of Small Molecules: Nitric Oxide

Cited by 8 publications

References 638 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

A New Member of the Growing Family of Interconvertible {RuNO}6,7,8 Species. Redox and Acid‐Base Characterization of [Ru((CH2py)2Me[9]aneN3)(NO)]n+

Stable Bimetallic FeII/{Fe(NO)2}9 Moiety Derived from Reductive Transformations of a Diferrous-dinitrosyl Species

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A New Member of the Growing Family of Interconvertible {RuNO}^6,7,8 Species. Redox and Acid‐Base Characterization of [Ru((CH₂py)₂Me[9]aneN₃)(NO)]ⁿ⁺

Stable Bimetallic Fe^II/{Fe(NO)₂}⁹ Moiety Derived from Reductive Transformations of a Diferrous-dinitrosyl Species