Metathesis and reduction reactions of nitroso compounds with metal carbenes and metal carbonyls

Herndon, James W.; Mcmullen, L. A.

doi:10.1016/0022-328x(89)80121-4

Cited by 29 publications

(10 citation statements)

References 44 publications

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“…Nitrosoarenes were found to be good substrates for the QC transfer reactions of [Ru(Por)(QC)], and the reactions led to the isolation of nitrones in up to 90% yield (Table ). These reactions contrast with previously reported stoichiometric reactions of metal–carbene complexes (CO) 5 MC(OMe)Ph (M = Cr, W) with nitrosoarenes (such as PhNO) to give metathesis-like products (such as OC(OMe)Ph and/or PhNC(OMe)Ph), rather than carbene transfer product nitrones. There is also a previous report on the stoichiometric reaction of iron–carbene complex [Cp(CO) 2 FeCHAr] + (Ar = p -C 6 H 4 OMe) with nitrosoarenes (such as PhNO), which gave iron–nitrone complexes without resulting in the isolation of nitrones …”

Section: Discussioncontrasting

confidence: 99%

Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom Transfer Reactions

Wang

Wan

et al. 2019

J. Am. Chem. Soc.

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Reactivity study of novel metal carbene complexes can offer new opportunities in catalytic carbene transfer reactions as well as in other synthetic protocols. Metal complexes with quinoid carbene (QC) ligands are assumed to be key intermediates in a variety of metal-catalyzed QC transfer reactions using diazo quinones, which demands development of the chemistry of QC transfer of well characterized metal–QC complexes. Herein we report the isolation and QC transfer of ruthenium porphyrins [Ru(Por)(QC)] which contribute the first examples of (i) structurally characterized metal–QC complex (by X-ray crystallography) and (ii) isolated metal–QC complex that undergoes QC transfer reaction. The complexes [Ru(Por)(QC)] were prepared from reaction of [Ru(Por)(CO)] with diazo quinones and exhibited dual reactivity, i.e., hydrogen atom transfer (HAT) as well as QC transfer. The stoichiometric QC transfer reactions from these Ru–QC complexes to nitrosoarenes (ArNO) afforded nitrones in up to 90% yield, and the corresponding catalytic reactions were also developed. Both the stoichiometric and catalytic reactions for a series of QC ligands bearing electron-donating and -withdrawing substituents showed a reverse substituent effect on the QC transfer reactivity. Complexes [Ru(Por)(QC)] are also reactive toward C–H and X–H (X = N, S) bonds and can catalyze aerobic oxidation of 1,4-cyclohexadiene; their stoichiometric HAT reactions with unsaturated hydrocarbons gave product yields of up to 88%. The unique dual reactivity and electronic feature of [Ru(Por)(QC)] were studied by spectroscopic means and density functional theory (DFT) calculations.

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Section: Discussioncontrasting

confidence: 99%

Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom Transfer Reactions

Wang

Wan

et al. 2019

J. Am. Chem. Soc.

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“…N ‐nitrosophenylhydroxylamine ammonium salt (cupferron) and lead tetraacetate were purchased from Sigma–Aldrich and were used as received. Nitrosobenzene and 2‐methylnitrosobenzene were purchased from Aldrich, whereas 4‐methyl‐,26 4‐methoxy‐,27 4‐chloro‐,28 4‐bromo‐28 and 4‐cyano‐29 nitrosobenzenes were prepared according to literature reports. BDE calculations were performed by means of the Gaussian 03 package30 on an IBM SP5 supercomputer at Cineca Supercomputing Center (via Magnanelli 6/3, I‐40033 Casalecchio di Reno, Bologna, Italy; http://www.cineca.it/HPSystems).…”

Section: Methodsmentioning

confidence: 99%

Reactions of Nitrosoarenes with Nitrogen Monoxide (Nitric Oxide) and Nitrogen Dioxide: Formation of Diarylnitroxides

et al. 2008

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Keywords: Nitrosoarenes / Nitrogen oxides / Diazonium salts / DiarylnitroxidesNitrosoarenes react with nitrogen monoxide (nitric oxide) at room temperature and in aprotic media to afford the corresponding diarylnitroxides by the intermediate formation of N-nitrosoarylnitroxides. However, these latter spin adducts, in contrast with literature reports, have never been detected by us. N-nitrosophenylnitroxide is obtained only in the oxidation of the ammonium salt of N-nitrosophenylhydroxylamine (cupferron) with trace amounts of lead tetraacetate. However, it evolves with time to diphenylnitroxide, as demonstrated by following the reaction course in the ESR cavity. On a macroscale level, the reaction between nitrosobenzene

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“…4-Nitrosobenzonitrile (4b). Using method B and 3b in diethyl ether, the crude product was obtained in 99% yield and was used without further purification after spectral and chromatographic comparison with an authentic sample …”

Section: Methodsmentioning

confidence: 99%

“…Using method B and 3b in diethyl ether, the crude product was obtained in 99% yield and was used without further purification after spectral and chromatographic comparison with an authentic sample. 26 2-(4-Nitrosophenyl)-1,1-dicyanoethylene (4c). Using method B and 3c in THF, the crude product was obtained in 82% yield: mp 122-124 °C; 1 H NMR (DMSO-d6) δ 8.70 (s, 1H, vinyl), 8.24 (d, 2H, J ) 9 Hz, Ar), 8.13 (d, 2H, J ) 9 Hz, Ar); IR (KBr) 2230, 1592, 1566, 1421, 1297 cm -1 ; EI MS m/z 183 (M + ).…”

Section: -(4-(hydroxylamino)phenyl)-11-dicyanoethylene (3c)mentioning

confidence: 99%

Synthesis of Aryl Nitroso Derivatives by tert-Butyl Hypochlorite Oxidation in Homogeneous Media. Intermediates for the Preparation of High-Hyperpolarizability Chromophore Skeletons

Davey

Lee²,

Miller³

et al. 1999

J. Org. Chem.

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Metathesis and reduction reactions of nitroso compounds with metal carbenes and metal carbonyls

Cited by 29 publications

References 44 publications

Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom Transfer Reactions

Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom Transfer Reactions

Reactions of Nitrosoarenes with Nitrogen Monoxide (Nitric Oxide) and Nitrogen Dioxide: Formation of Diarylnitroxides

Synthesis of Aryl Nitroso Derivatives by tert-Butyl Hypochlorite Oxidation in Homogeneous Media. Intermediates for the Preparation of High-Hyperpolarizability Chromophore Skeletons

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