10026-04-7 ASSISTANCE NUCLEOPHILE DANS DES REACTIONS DE REDUCTION D'ORGANOHALOGENO- ET HALOGENO-GERMANES PAR DES REDUCTEURS DOUX R3M(IVB)-H ET RCHO: GERMYLANIONS, DERIVES FONCTIONNELS DU GERMANIUM

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Catalytic activity of nuclophiles such as tertiary amines and diazo derivatives in the reduction of halogermanes by means of gentle reductive agents, such as R3M(IVB)-H or RCHO, has been shown.In the particular case of enolisable aldehyde, a competition between nucleophilic substitution at the metal and germanium-halogen bond reduction has been observed.Transposition of enoxygermanes formed through the substitution process, leads to β-germylaldehydes. https://www.lookchem.com/CASDataBase_10026-04-7.htm

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100-64-1 On the Oxidation of Hydroxylamines with o -Iodoxybenzoic Acid (IBX)

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o -Iodoxybenzoic acid (IBX) is confirmed as a powerful tool for the oxidation of hydroxylamines. The synthetic route is demonstrated as efficient and user friendly, and is exploited on various carbohydrate-derived N,N-disubstituted hydroxylamines (cyclic, acyclic, and functionalized ones), affording the corresponding nitrones in good yields and regioselectivity. N-Monosubstituted hydroxylamines revealed an interesting divergent behavior depending on the reaction conditions. While IBX oxidation in dimethyl sulfoxide at 45 °C furnished oximes as reported, the oxidation in dichloromethane at room temperature afforded efficiently the unusual corresponding nitroso dimers. https://www.lookchem.com/CASDataBase_100-64-1.htm
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75-01-4 Nickel(I) Octaethylisobacteriochlorin Anion. An Exceptional Nucleophile. Reduction and Coupling of Alkyl Halides by Anionic and Radical Processes. A Model for Factor F-430

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Nickel(I)octaethylisobacteriochlorin anion (Ni(I)OEiBC - ) reacts extremely rapidly with aliphatic halides and methyl tosylate in homogeneous DMF solution.The reactivity sequence, CH3 > primary > secondary tertiary, and the rate law accord with an S N 2-like process for the carbon-halogen bond scission.However, the main products of the reactions derive from free radicals.The rate for methyl chloride is 2000 times faster than the corresponding reaction with the super nucleophile Co(I)B12 s -1 and the rate constant for isopropyl bromide is 350 times greater than that observed with CpFe(CO)2 - .The results indicate NiOEiBC - is the fastest nucleophile on record.Studies of the influence of solvent and reactant deuteration and the influence of anion and radical scavengers upon the product distribution suggest the intermediacy of at least one and possibly two nickel alkyls of fleeting lifetime.A novel explanation for the unusual speed of these reactions is put forward.It entails the...
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100-40-3 ?-Arene Complexes of Nickel(II). Synthesis (from Metal Atoms) of (?-Arene)bis(pentafluorophenyl)nickel(II). Properties, ?-Arene Lability, and Chemistry

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A new series of transition-metal-?-arene complexes has been prepared by a metal atom synthetic method.The deposition of Ni vapor, C6F5Br, and arenes has prodused high yields of (C6F5)2Ni-?-arene complexes.A variety of ?-arene ligands are η 6 bound by the (C6F5)2Ni moiety, resulting in soluble highly labile materials, where the ?-arene ligand is exchangeble at room temperature.These complexes have not been isolable when ?-bonding ligands other then C6F5 have been employed.The formation of the ?-toluene complex proceeds through a pseudostable C6F5NiBr species that can be trapped at -80 deg C with R3P but decomposes by reductive elimination of CF5-CF5 in the absence of R3P or electron-rich arenes.It is likely that C6F5NiBr-?-arene is formed initially, which then disproportionates to (C6F5)2Ni-?-arene and NiBr2.Due to the high lability of the ?-arene ligand, these complexes possess a rich chemistry.Displacement of the ?-arene ligand can bee carried out cleanly and in high yield by P(Et)3,...
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