Rhodium complexes nitro

Oxidation of Alkenes by Palladium(II)- and Rhodium(III)-Nitro Complexes 373... 

The cationic rhodium(III)-nitro complex [(MeCN)4RhN02]2+(BF4)2 also oxidizes ethylene and 1 -octene to acetaldehyde and 2-octanone, respectively. However, no catalytic oxidation takes place in the presence of dioxygen.477... 

The tris(ethylenediamine) chromium (III) ion was first resolved by Werner6 by means of sodium 3-nitro-(+)-camphor. What has been said concerning the resolution of the corresponding rhodium compound holds true of the chromium compound, except that for the chromium compound the solubility difference of the diastereoisomeric chloride (+)-tartrates is so small that a resolution via these diastereoisomers has not been achieved.5,6 The method reported here is essentially the same as the one described for the rhodium complex but with minor alterations... 

NOCgHj, Benzoyl isocyanide, chromium complex, 26 32,34,35 N0C,3H,3, Formanide, N-(l-(l-naphthal-enyl)ethyll-, rhenium complex, 29 217 NOPCjsHjj, Benzamide. 2-(diphenylphos-phino)-N-phenyl-, 27 324 NOPCjjHjj, Benzamide, Af-[2-(diphenyl-phosphino)phenyl]-, 27 323 NO2CH3, Methane, nitro-, antimony complex, 29 113 cobalt complex, 29 114 NOjCjHj, 4-Pyridinecarboxylic acid, rhodium complex, 27 292 NO2P2C3JH33, Phosphorus(l-t-), p-nitrido-bis(triphenyl-, acetate, 27 296 NO2SC3H7, L-Cysteine, molybdenum complex, 29 255,258... 

For nitromesitylene in dichlorobenzene at 120 °C and 1 atm, k = 1.3 10, AH = 18 kcal mol and AS = - 30 cal K. Large substituents in the or//io position of the nitro compound accelerate the reaction, a situation already described in the case of some palladium and ruthenium systems [26, 38,43] (see paragraph 6.3.1. for a discussion of this effect). If other rhodium complexes were used as catalyst precursors, [Rh(CO)2(Cl)]2 was anyway formed by ligand exchange with the molybdenum chloride [207]. 

There are rather few water-soluble hydrogenation catalysts. A number of rhodium complexes derived from ligands such as (PH2PCH2CH2)2NC0C6H4S03" are active in this way. " Catalysts have been developed for hydrogenation of ketonescarboxylic acids/ esters/ nitriles/ and nitro compounds. 

The nitro group is a strong electron-withdrawing group that has versatile synthetic use. Nitrodiazoacetates 149 yielded nitrocyclopropanes 150 when treated with rhodium complexes... 

Secondary amines can be added to certain nonactivated alkenes if palladium(II) complexes are used as catalysts The complexation lowers the electron density of the double bond, facilitating nucleophilic attack. Markovnikov orientation is observed and the addition is anti An intramolecular addition to an alkyne unit in the presence of a palladium compound, generated a tetrahydropyridine, and a related addition to an allene is known.Amines add to allenes in the presence of a catalytic amount of CuBr " or palladium compounds.Molybdenum complexes have also been used in the addition of aniline to alkenes. Reduction of nitro compounds in the presence of rhodium catalysts, in the presence of alkenes, CO and H2, leads to an amine unit adding to the alkene moiety. An intramolecular addition of an amine unit to an alkene to form a pyrrolidine was reported using a lanthanide reagent. 

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