- Triazenido Complexes of Titanocene(III)
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Triazenido metal complexes have been extensively investigated for more than a century, especially transition metal complexes. However, in each of the known examples for titanium, the oxidation state of the metal is +4. Therefore, we sought to prepare a complex containing titanium(III). To achieve this goal, triazenes RNNN(H)R′ (1R, with R = R′ = Ph; Dipp; Ter; R = Mes*, R′ = mTol) and triazenido salts Li[RNNNR′] (R = R′ = Ter; R = Ter, R′ = mTol) were prepared. These were treated with suitable titanium precursors either from reaction with the alkyne complex Cp2Ti(η2-Me3SiC2SiMe3) or in a salt metathesis with [Cp2TiCl]2 to give chelate complexes of the type Cp2Ti[RNNNR′] (2R, with R =R′ = Ph; Dipp; R = Ter; R′ = mTol). The synthesis, reactivity, and bonding of the titanocene triazenides were studied.
- Beweries, Torsten,Rei?, Fabian,Rothe, Julia,Schulz, Axel,Villinger, Alexander
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- Thermal cis-to-trans isomerisation of triazene dyes in doped polymer films
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The kinetics of the thermal conversion of the cis to the trans isomeric forms of 1,3-diphenyltriazene and 1-phenyltriazenes derived from cyclic amines were determined in both poly(methyl methacrylate) and polystyrene doped films in the glassy state, using
- Tabone, Ryan,Barra, Mónica
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experimental part
p. 180 - 186
(2011/01/12)
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- Reactions of Nitric Oxide with Amines in the Presence of Dioxygen
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Nitric oxide (NO), a multifaceted bioregulatory agent and an environmental pollutant, can effectively convert aromatic amines to the corresponding triazenes under aerobic conditions, but not under anaerobic conditions.Nucleic acid bases and nucleosides are also determinated via hydrolysis of the diazonium ion products with exposure to aerobic NO solution.A peroxynitrite radical or nitrogen dioxide is suggested to be the ultimate reactive species.
- Nagano, Tetsuo,Takizawa, Hiromasa,Hirobe, Masaaki
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p. 8239 - 8242
(2007/10/02)
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- A New Reaction of Aryl Isocyanates with Nitrite Ion
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Reaction of nitrite ion with excess aryl isocyanate in organic solvents at 0 deg C rapidly produces 1,3-diaryltriazenes in good yields via an aryldiazotate ion intermediate reacting with a second molecule of the aryl isocyanate.
- Botting, Nigel P.,Challis, Brian C.
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p. 1585 - 1586
(2007/10/02)
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- PHOTOCHEMISTRY OF 1,3-DIPHENYLTRIAZENE IN VARIOUS MEDIA. I: PHOTOLYSIS IN LIQUID SOLUTIONS.
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1,3-Diphenyltriazene has been irradiated at 360 nm in various liquid solutions. Reversible trans-cis photoisomerization has been detected in solvents which do not form hydrogen bonds. Irreversible photolysis is observed with an appreciable amount of cage recombination products in all solvents. This reaction is well suited for a study in solid environments.
- Baro,Dudek,Luther,Troe
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p. 1155 - 1161
(2007/10/02)
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- Treatment of aromatic amines with gas mixtures derived from the oxidation of ammonia to effect diazotization/coupling
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1,3-Diaryl triazenes, e.g., 1,3-diphenyltriazene, intermediates in the synthesis of aromatic diamines, e.g., p-phenylenediamine, are prepared by catalytically oxidizing ammonia, and subsequently the resulting nitric oxide, with a gas comprising diluted molecular oxygen, e.g., air, so as to produce a gas mixture containing dilute NOx, i.e., NO2 preferably admixed with NO, x being (1 + n), wherein n is the NO2 fraction of the NOx ; and contacting the gas mixture, preferably at a temperature in the range of about from 25° to 350° C., with excess primary aromatic monoamine, e.g., aniline, so as to result in a monoamine temperature in the range of about from 25° to 90° C., preferably 40° to 60° C., during contact. Highest yields of triazene are obtained when the x in NOx is about from 1.3 to 1.7, and the amount of NOx gas mixture contacted with the monoamine and the time of contact are such that at least about 60% by weight of the monoamine remains unconsumed. A gas mixture temperature just prior to gas contact with the liquid monoamine in the range of about from 110° to 275° C. is more preferred under certain circumstances.
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