Controlled nitrene transfer from a tyrosinase-like arylnitroso–copper complex

Askari, Mohammad S.; Orio, Maylis; Ottenwaelder, Xavier

doi:10.1039/c5cc02806j

Cited by 17 publications

(25 citation statements)

References 42 publications

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“…While the symmetry of the complexes is different and some complexes have multiple vibrational modes involving the NO stretch, the NO stretching energy decreases from 1315/1392 cm −1 for 3 NMe 2 to 1226 cm −1 for 3 Br to 875 cm −1 for 3 NO 2 . 25 69 257 Hence, the lack of a signal in a standard acquisition window 258 can be used as a local diagnostic of radical character on N. 259 Overall, the NMR data confirm, in solution, the assignments 260 that were made in the solid state.…”

Section: ■ Introductionmentioning

confidence: 65%

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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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Section: ■ Introductionmentioning

confidence: 65%

“…The complex with the most electron-poor ArNO moiety, 3 NO 2 , was characterized in a previous communication. 25 It is a dinuclear species of the formula [TMPDCu II (μ-η 2 :η 2 -PhNO 2− )(μ-TfO)Cu II TMPD](TfO), where 2 NO 2 is reduced by 2e (N−O = 1.456 Å) and both Cu centers are in the 2+ oxidation state.…”

Section: ■ Introductionmentioning

confidence: 99%

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

et al. 2020

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“…For instance, coordination of two β‐diketiminato nickel(I) fragments to a nitrosoarene leads to {[Me 2 NN]Ni} 2 (μ‐η 2 :η 2 ‐ONAr) (Ar=3,5‐Me 2 C 6 H 3 ) with a N−O distance of 1.440(4) Å, considerably longer than in free aryl nitroso compounds (1.21–1.23 Å) . A dinuclear copper complex LCu(μ‐η 2 :η 2 ‐ONAr)CuL (L=tetramethylpropylenediamine, Ar=4‐NO 2 ‐C 6 H 4 ) with a N−O distance of 1.457(9) Å has been recently reported to possess a similar electronic structure as found in dicopper‐(μ‐η 2 :η 2 ‐peroxo) species . The electron‐rich β‐diketiminato Co I complex [Me 2 NN]Co(η 6 ‐toluene) provides an extreme case of N−O bond activation, completely cleaving the ArN=O bond to give {[Me 2 NN]Co} 2 (μ‐O)(μ‐NAr) (Ar=3,5‐Me 2 C 6 H 3 ) …”

Section: Figurementioning

confidence: 99%

“…[2b,9] Fori nstance,c oordination of two b-diketiminato nickel(I) fragments to an itrosoarene leads to {[Me 2 NN]Ni} 2 (m-h 2 :h 2 -ONAr) (Ar = 3,5-Me 2 C 6 H 3 ) [9a] with aN ÀOd istance of 1.440(4) , considerably longer than in free aryl nitroso compounds (1.21-1.23 ). [10] Herein we report the successful isolation of an unusual mononuclear b-diketiminato [Ni II ](h 2 -ONPh)C /À complex that features an itrosobenzene radical anion ligand. [10] Herein we report the successful isolation of an unusual mononuclear b-diketiminato [Ni II ](h 2 -ONPh)C /À complex that features an itrosobenzene radical anion ligand.…”

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Redox Non‐Innocence of Nitrosobenzene at Nickel

et al. 2016

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Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox-active nitric oxide derivative. Capture of nitrosobenzene at the electron-deficient β-diketiminato nickel(I) complex [(i) Pr2 NNF6 ]Ni results in reduction of the PhNO ligand to a (PhNO)(./-) species coordinated to a square planar Ni(II) center in [(i) Pr2 NNF6 ]Ni(η(2) -ONPh). Ligand centered reduction leads to the (PhNO)(2-) moiety bound to Ni(II) supported by XAS studies. Systematic investigation of structure-reactivity patterns of (PhNO)(./-) and (PhNO)(2-) ligands reveals parallels with superoxo (O2 )(./-) and peroxo (O2 )(2-) ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand.

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“…[2b] Ad inuclear copper complex LCu(m-h 2 :h 2 -ONAr)CuL (L = tetramethylpropylenediamine,Ar= 4-NO 2 -C 6 H 4 )with aN À Odistance of 1.457(9) h as been recently reported to possess as imilar electronic structure as found in dicopper-(m-h 2 :h 2 -peroxo) species. [10] Herein we report the successful isolation of an unusual mononuclear b-diketiminato [Ni II ](h 2 -ONPh)C /À complex that features an itrosobenzene radical anion ligand. Interestingly, one-electron reduction of this [Ni II ](h 2 -ONPh)C /À species is ligand-centered and provides a[ Ni II ](h 2 -ONPh) 2À complex, which serves as am odel of ad oubly deprotonated hydroxylamine ligand.…”

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Redox Non‐Innocence of Nitrosobenzene at Nickel

et al. 2016

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Nitrosobenzene (PhNO) serves as astable analogue of nitroxyl (HNO), ab iologically relevant, redox-active nitric oxide derivative.C apture of nitrosobenzene at the electrondeficient b-diketiminato nickel(I) complex [ i Pr 2 NN F6 ]Ni results in reduction of the PhNO ligand to a(PhNO)C /À species coordinated to asquare planar Ni II center in [ i Pr 2 NN F6 ]Ni(h 2 -ONPh). Ligand centered reduction leads to the (PhNO) 2À moiety bound to Ni II supported by XAS studies.S ystematic investigation of structure-reactivity patterns of (PhNO)C /À and (PhNO) 2À ligands reveals parallels with superoxo (O 2 )C /À and peroxo (O 2 ) 2À ligands,r espectively,a nd forecasts reactivity patterns of the more transient HNO ligand.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.

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Controlled nitrene transfer from a tyrosinase-like arylnitroso–copper complex

Cited by 17 publications

References 42 publications

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

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

Redox Non‐Innocence of Nitrosobenzene at Nickel

Redox Non‐Innocence of Nitrosobenzene at Nickel

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