Interactions of Nitrosoalkanes/arenes, Nitrosamines, Nitrosothiols, and Alkyl Nitrites with Metals

Xu, Nan; Richter‐Addo, George B.

doi:10.1002/9781118869994.ch06

Cited by 7 publications

(13 citation statements)

References 298 publications

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“…Whereas heme HNO model complexes are generally unstable at room temperature, ,,, ferrous heme nitrosoalkane complexes are typically very stable . With the idea of creating a more stable version of 5 with similar spectroscopic parameters, and determining whether 5 is indeed protonated at the NO – ligand, we therefore attempted to generate a corresponding nitrosoalkane complex by addition of CH 3 + sources to 2 .…”

Section: Results and Analysismentioning

confidence: 96%

“…Whereas heme HNO model complexes are generally unstable at room temperature, 50,52,96,97 ferrous heme nitrosoalkane complexes are typically very stable. 98 With the idea of creating a more stable version of 5 with similar spectroscopic parameters, and determining whether 5 is indeed protonated at the NO − ligand, we therefore attempted to generate a corresponding nitrosoalkane complex by addition of CH 3 + sources to 2. Although weaker alkylating agents such as methyl iodide resulted in no reaction, upon addition of trimethyloxonium tetrafluoroborate to 2, conversion to a new species occurs, which we assign as the methylated complex (6).…”

Section: Table 3 Best Structural Fits Of the Exafs Datamentioning

confidence: 99%

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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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Section: Results and Analysismentioning

confidence: 96%

Section: Table 3 Best Structural Fits Of the Exafs Datamentioning

confidence: 99%

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

et al. 2018

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“…The interaction of nitrosoarenes (ArNO) with metal centers has drawn much attention because of its relevance to biological pathways − and catalytic C–N bond formation processes. − Chemists now have a good understanding of the geometric structure of transition metal/nitrosoarene complexes. , In addition, ArNO species are redox-noninnocent ligands, − which portends a large landscape of electronic structures and reactivity types upon interaction with redox-active metal ions.…”

Section: Introductionmentioning

confidence: 99%

Tuning Inner-Sphere Electron Transfer in a Series of Copper/Nitrosoarene Adducts

et al. 2020

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A series of copper/nitrosoarene complexes were created that mimic several steps in biomimetic O 2 activation by copper(I). The reaction of the copper(I) complex of N,N,N′,N′tetramethypropylenediamine with a series of para-substituted nitrosobenzene derivatives leads to adducts in which the nitrosoarene (ArNO) is reduced by zero, one, or two electrons, akin to the isovalent species dioxygen, superoxide, and peroxide, respectively. The geometric and electronic structures of these adducts were characterized by means of X-ray diffraction, vibrational analysis, ultraviolet−visible spectroscopy, NMR, electrochemistry, and density functional theory (DFT) calculations. The bonding mode of the NO moiety depends on the oxidation state of the ArNO moiety: κN for ArNO, mononuclear η 2-NO and dinuclear μ-η 2 :η 1 for ArNO •− , and dinuclear μ-η 2 :η 2 for ArNO 2−. 15 N isotopic labeling confirms the reduction state by measuring the NO stretching frequency (1392 cm −1 for κN-ArNO, 1226 cm −1 for η 2-ArNO •− , 1133 cm −1 for dinuclear μ-η 2 :η 1-ArNO •− , and 875 cm −1 for dinuclear μ-η 2 :η 2 for ArNO 2−). The 15 N NMR signal disappears for the ArNO •− species, establishing a unique diagnostic for the radical state. Electrochemical studies indicate reduction waves that are consistent with one-electron reduction of the adducts and are compared with studies performed on Cu-O 2 analogues. DFT calculations were undertaken to confirm our experimental findings, notably to establish the nature of the charge-transfer transitions responsible for the intense green color of the complexes. In fine, this family of complexes is unique in that it walks through three redox states of the ArNO moiety while keeping the metal and its supporting ligand the same. This work provides snapshots of the reactivity of the toxic nitrosoarene molecules with the biologically relevant Cu(I) ion. 47 usually too oxidative to be stable above −60°C.

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“…So far, chemists have reported a variety of stable transition-metal complexes bearing PhNO and its derivatives in different binding modes. − Although the bonding pattern of the PhNO ligand can readily be confirmed by X-ray diffraction analysis, it is usually very difficult to unambiguously assign its oxidation state, viz. PhNO 0 , PhNO •– , or PhNO 2– due to its redox noninnocent character. , Among numerous monometallic complexes, PhNO commonly adopts a η 1 - N , η 1 - O , or η 2 - N , O coordination fashion.…”

Section: Introductionmentioning

confidence: 99%

Generation of a Sulfinamide Species from Facile N–O Bond Cleavage of Nitrosobenzene by a Thiolate-Bridged Diiron Complex

Yang

Wang

et al. 2021

J. Am. Chem. Soc.

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The activation of nitrosobenzene promoted by transition-metal complexes has gained considerable interest due to its significance for understanding biological processes and catalytic C–N bond formation processes. Despite intensive studies in the past decades, there are only limited cases where electron-rich metal centers were commonly employed to achieve the N–O or C–N bond cleavage of the coordinated nitrosobenzene. In this regard, it is significant and challenging to construct a suitable functional system for examining its unique reactivity toward reductive activation of nitrosoarene. Herein, we present a {Fe2S2} functional platform that can activate nitrosobenzene via an unprecedented iron-directed thiolate insertion into the N–O bond to selectively generate a well-defined diiron benzenesulfinamide complex. Furthermore, computational studies support a proposal that in this concerted four-electron reduction process of nitrosobenzene the iron center serves as an important electron shuttle. Notably, compared to the intact bridging nitrosoarene ligand, the benzenesulfinamide moiety has priority to convert into aniline in the presence of separate or combined protons and reductants, which may imply the formation of the sulfinamide species accelerates reduction process of nitrosoarene. The reaction pattern presented here represents a novel activation mode of nitrosobenzene realized by a thiolate-bridged diiron complex.

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Interactions of Nitrosoalkanes/arenes, Nitrosamines, Nitrosothiols, and Alkyl Nitrites with Metals

Cited by 7 publications

References 298 publications

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

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

Tuning Inner-Sphere Electron Transfer in a Series of Copper/Nitrosoarene Adducts

Generation of a Sulfinamide Species from Facile N–O Bond Cleavage of Nitrosobenzene by a Thiolate-Bridged Diiron Complex

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Interactions of Nitrosoalkanes/arenes, Nitrosamines, Nitrosothiols, and Alkyl Nitrites with Metals

Cited by 7 publications

References 298 publications

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

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

Tuning Inner-Sphere Electron Transfer in a Series of Copper/Nitrosoarene Adducts

Generation of a Sulfinamide Species from Facile N–O Bond Cleavage of Nitrosobenzene by a Thiolate-Bridged Diiron Complex

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Product

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

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