Die Katalyse des Hydroxylamins

Kurten, Albin; Wengefeld, Friedrich

doi:10.1002/zaac.19241400120

Cited by 11 publications

(1 citation statement)

References 13 publications

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“…Hydroxylamine is readily oxidized in alkaline solution by cupric sulfate, yielding nitrous oxide almost exclusively (8,11). In the present exploratory work with the cupric hydroxide-cupric oxide system, the precipitate was prepared at 25°C.…”

Section: Cupric Hydroxidementioning

confidence: 99%

Influence of Age and Surface Conditions on the Reactivity of Certain Precipitates.

James¹

1942

J. Phys. Chem.

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Section: Cupric Hydroxidementioning

confidence: 99%

Influence of Age and Surface Conditions on the Reactivity of Certain Precipitates.

James¹

1942

J. Phys. Chem.

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Dipicolinato(hydroxylamido‐O,N)(nitrosyl)aquavanadat — ein Nitrosylkomplex des Vanadiums mit „side on”︁ koordiniertem Hydroxylamin

et al. 1978

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Vanadium(v) wird in alkalischer oder saurer wa0rige.r L 6 sung durch Hydroxylamin reduziert; je nach Reaktionsbedingungen konnen dabei N2, N 2 0 und NO (sowie NH3) entstehen"]. In saurer Losung wurde die Existenz eines Vanadium(vkHydroxy1amin-1: 1-Komplexes spektroskopisch nachgewiesen [2], der aber nicht isoliert wurde.Das funffach koordinierte cis-Dioxo(dipico1inato)vanadat(v)-Ion ( 1 )I3] reagiert rnit Hydroxylammoniumchlorid in schwach saurer waI3riger Losung (25OC) unter Bildung eines farblosen Neutralkomplexes (2), der aufgrund seiner analytischen und IR-spektroskopischen Daten als p-0x0-bis[oxo(dipicolinato)(hydroxylamin-N)vanadium(v)] formuliert werden kann.

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Dipicolinato(hydroxylamido‐O,N)(nitrosyl)aquavanadate—A Nitrosyl Complex of Vanadium with “side on” Coordinated Hydroxylamine

Wieghardt

Quilitzsch

Nuber

et al. 1978

Angew. Chem. Int. Ed. Engl.

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coordinated dipicolinato ligand (dipi~)'~] and a strong band at 1530cm-' which we assign to a v(N=O) vibration. Vanadium(v) undergoes reduction with hydroxylamine in alkaline or acidic aqueous solution; depending upon the reaction conditions N2, N20, and NO (as well as NH3) may be formed [']. A vanadium(v)-hydroxylamine 1 : 1 complex has been shown to exist in acidic solution[21 but so far has not been isolated. Dipicolinato(h ydrox ylamido-O,N)(nitrosyl)aquaReaction of five-coordinated cis-dioxo(dipico1inato)vanadate(v) ion with hydroxylammonium chloride in weakly acidic solution (25 "C) affords a colorless neutral complex ( 2 ) , which on the basis of its analytical and IR spectroscopic data can be formulated as p-0x0-bis[oxo(dipicolinato)(hydroxylamine-N)vanadium(v)].In alkaline solution (I) reacts quantitatively with hydroxylamine (1:2) without evolution of gas (!) to give deep-red solutions. Addition of solid KCI or CsCl yields air stable crystalline potassium and cesium salts, respectively. The IR spectra of these salts show the characteristic bands of the The structure of the anion (3) was determined by X-ray spectroscopy (Fig. 1). Cs[V(dipic)(H2NO)(NO)(H20)] '2 H2O crystallizes in the orthorhombic space group DM-Pcmb with a=839.4(3), b=884.3(2), c= 1936.1(6)pm, 2=8. Refinement with structure factors of 1260 observed independent reflections [I > 2.58 o(I)] converged to an unweighted R value of 5.9 %.The positions of the H atoms could not be determined because of the poor quality of the crystals (platelets). The central vanadium atom is surrounded by a distorted pentagonal-bipyramidal array of tridentate dipicolinate ligands, a bidentate hydroxylamido ligand and-in the axial positions-a nitrosyl and an aqua ligand (the formal coordination number is 7) (Fig. 1). The hydroxylamido ligand is most probably coordinated as H2N-O-[51. The nitrosyl group is almost linearly coordinated, and the V-N2 bond length is relatively short. Analogous bonding has been reported for the [V(CN),NO]"-ion ["]. The H2NO-ligand is coordinated "side on" via the 0-and the N-atom, the N3-05 distance corresponds to that of the usual N-0 single bond length.The smooth reaction course in alkaline medium and the lack of formation of gaseous reaction products are considered to be indicative of an intramolecular transfer of two electrons from N-coordinated hydroxylamine to Vv (formally, V"' and NOe are formed). This is supported by the following experiment: Reaction of the V"'-complex ( 4 ) with hydroxylamine in alkaline solution likewise affords (3):351

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Die Katalyse des Hydroxylamins

Abstract: Es wurde die Einwirkung von Vanadin‐, Molybdänsaure, Kupfer‐ und Eisensalz auf Hydroxylamin untersucht.

Cited by 11 publications

References 13 publications

Influence of Age and Surface Conditions on the Reactivity of Certain Precipitates.

Influence of Age and Surface Conditions on the Reactivity of Certain Precipitates.

Dipicolinato(hydroxylamido‐O,N)(nitrosyl)aquavanadat — ein Nitrosylkomplex des Vanadiums mit „side on”︁ koordiniertem Hydroxylamin

Dipicolinato(hydroxylamido‐O,N)(nitrosyl)aquavanadate—A Nitrosyl Complex of Vanadium with “side on” Coordinated Hydroxylamine

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