100-50-5Relevant articles and documents
SELECTIVE HYDROFORMYLATION OF CYCLODIENES TO CYCLOALKENECARBOXALDEHYDES USING CATALYSTS DERIVED DIRECTLY FROM Rh VAPOUR AND CYCLODIENES
Salvadori, Piero,Vitulli, Giovanni,Raffaelli, Andrea,Lazzaroni, Raffaello
, p. 351 - 356 (1983)
Cocondensation of Rh atoms with cyclodienes at liquid nitrogen temperature yields Rh complexes, thermally stable in excess of the ligand, which are good catalysts for the selective hydroformylation of cyclodienes to cycloalkenecarboxaldehydes.
Highly Efficient Regeneration of Carbonyl Compounds from Oximes, Tosylhydrazones, 1,3-Dithiolanes, and 1,3-Dithianes Using Cupric Nitrate Supported on Silica Gel
Lee, Jong Gun,Hwang, Je Pil
, p. 507 - 508 (1995)
Cupric nitrate supported on silica gel is exceptionally efficient in regenerating aldehydes and ketones from oximes, tosylhydrazones, 1,3-dithiolanes, and 1,3-dithianes.
Visible-Light-Driven Photocatalytic Oxidation of Organic Chlorides Using Air and an Inorganic-Ligand Supported Nickel-Catalyst Without Photosensitizers
Yu, Han,Wang, Jingjing,Zhai, Yongyan,Zhang, Mengqi,Ru, Shi,Han, Sheng,Wei, Yongge
, p. 4274 - 4279 (2018)
Engineering photoredox-triggered chemical transformation via visible light has been an emerging area in organic synthesis. However, most of the well-established photocatalysts are based upon either transition metal complexes involved with noble metals and organic ligands or photosensitive organic dyes, the development of pure inorganic molecular photocatalysts that could provide better stability and durability is greatly retarded. Herein we discover that the Anderson polyoxometalate (POM) Na4[NiMo6O18(OH)6] (1), which consists of pure inorganic framework built from a central NiII core supported by six MoVIO6 inorganic scaffold/ligands, can be used as a powerful photocatalyst. Upon irradiation with visible light (>400 nm), the compound can catalyze, in high efficiency, a wide range of reactions, including the oxidative cross-coupling reaction of chlorides with amines, as well as oxidation of chlorides using molecular oxygen, affording various imines, aldehydes, and ketones, respectively in high selectivity and good yields. Owing to the robust inorganic framework, this catalyst exhibits excellent stability during the catalysis and reusability with little loss of the catalytic activity, thus providing an alternative without use of complicated organic ligands and expensive noble metal-based photosensitizers.
Studies on Transition-Metal Oxo and Nitrido Complexes. Part 10. New Oxo-Ruthenium and Oxo-Osmium Pyridine Complexes, and Use of the Former as Catalysts for Oxidation of Alcohols
El-Hendawy, Ahmed M.,Griffith, William P.,Taha, Fatma I.,Moussa, Mahmoud N.
, p. 901 - 906 (1989)
The new complexes trans-(2+), trans-(2+), trans- (M=Ru or Os; X=Cl or Br; py= pyridine) and trans- are reported.Both tans-(2+) and trans- in CH2Cl2 are efficient oxidants for primary alcohols to aldehydes and secondary alcohols to ketones, and function catalytically, with N-methylmorpholine N-oxide (mmo) or n4> as co-oxidants.A simple preparation of trans- and the isolation of , , and OsO2L2(O2C6H10)> (L=pyridine N-oxide) are also reported. Complexes were characterised by Raman, i.r. and (1)H n.m.r.spectroscopy.
Rhodium-Catalyzed C,C-Double Bond Cleavage by Molecular Oxygen
Boennemann, Helmut,Nunez, Washington,Rohe, Dieter M. M.
, p. 177 - 185 (1983)
Acetylacetonatorhodiumolefin systems, allylrhodium complexes, or (Ph3P)3RhCl catalyzed the conversion of alkenes and molecular oxygen to carbonyl compounds via C=C-bond cleavage.For example, 2,3-dimethyl-2-butene was transformed into acetone.Butadiene and isoprene also undergo oxidative C=C-bond cleavage to form acrylaldehyde and related compounds.
Homogeneous green catalysts for olefin oxidation by mono oxovanadium(V) complexes of hydrazone Schiff base ligands
Monfared, Hassan Hosseini,Bikas, Rahman,Mayer, Peter
, p. 2574 - 2583 (2010)
Three mono oxovanadium(V) complexes of tridentate Schiff base ligands [VO(OMe)L'] (1), [VO(OMe)L2] (2) and [VO(OMe)L3] (3) obtained by monocondensation of 3-hydroxy-2-naphthohydrazide and aromatic o-hydroxyaldehydes have been synthesized (H2L2 - (E)-3-hydroxy-N′-(2-hydroxy-3-methoxybenzylidene)-2-naphthohydrazide, H2L2 - (E)-3-hydroxy-N′-(2-hydroxybenzylidene)-2- naphthohydrazide and H2L3 - (E)-N′-(5-bromo-2- hydroxybenzylidene)-3-hydroxy-2-naphthohydrazide). The complexes were characterized by spectroscopic methods in the solid state (IR) and in solution (UV-Vis, 1H NMR). Single crystal X-ray analyses were performed with 1 and 2. The catalytic potential of these complexes has been tested for the oxidation of cyclooctene using H2O2 as the terminal oxidant. The effects of various parameters including the molar ratio of oxidant to substrate, the temperature, and the solvent have been studied. The catalyst 2 showed the most powerful catalytic activity in oxidation of various terminal, cyclic and phenyl substituted olefins. Excellent conversions have been obtained for the oxidation of cyclic and bicyclic olefins.
Alkene Epoxidations Catalyzed by Iron(III), Manganese(III), and Chromium(III) Porphyrins. Effects of Metal and Porphyrin Substituents on Selectivity and Regiochemistry of Epoxidation
Traylor, Teddy G.,Miksztal, Andrew R.
, p. 7443 - 7448 (1989)
The products of epoxidation of norbornene, cyclohexene, and adamantylideneadamantane with pentafluoroiodobenzene using as catalysts variously substituted tetraphenylporphyrin complexes of chloroiron(III), chloromanganese(III), and chlorochromium(III) have been determined.All catalysts afforded the epoxide from adamantylideneadamantane, suggesting that the metallacycle intermediate, impossible in this case, is not required for epoxidation.The ratios of exo- to endo-epoxynorbornanes obtained from norbornene varied from about 1E3 for electropositively substituted Cr(III) complexes gradually through the Mn(III) and Fe(III) series to a value of about 6 for electronegatively substituted iron(III) porphyrins.Mechanisms ranging from limiting electrophilic addition to limiting electron transfer are proposed to account for these changes.The electronegatively substituted iron porphyrins show a greater tendency toward epoxidation rather than allylic oxidation and show more selectivity for cis-alkenes.
Olefin Oxidation Catalyzed by Electron Deficient Metallo-Porphyrin
Ogoshi, Hisanobu,Suzuki, Yasuhiko,Kuroda, Yasuhisa
, p. 1547 - 1550 (1991)
Olefin oxidations catalyzed by Fe or Mn complexes of 2,4,6,8-tetratrifluoromethyl-1,3,5,7-tetraethylporphyrin (TFTEP) using iodosobenzene as oxidant were investigated.Comparison of TFTEP with usual OEP/iodosobenzene systems shows that the electronic effec
Reduction of Organic Compounds with Rare-Earth Intermetallics Containing Absorbed Hydrogen
Imamoto, Tsuneo,Mita, Takeshi,Yokoyama, Masataka
, p. 5695 - 5699 (1987)
The hydrogenation of organic compounds with rare-earth intermetallic hydrides has been investigated.Alkynes,alkenes,aldehydes,ketones,nitriles,imines, and nitro compounds are hydrogenated in excellent yields with LaNi5H6 or LaNi4.5Al0.5H5 at 0-60 deg C.The present hydrogenation method has the following characteristic features. (1) The intermetallic compounds (alloys) are not poisoned by compounds containing an amino group or a halogen atom. (2) The alloys can be used repeatedly without decrease in activity. (3) The reaction conditions are mild, and selective hydrogenations of some organic functional groups can be achieved.The reaction mechanism of this hydrogenation is briefly discussed in terms of stereochemistry and H/D exchange reactions.
Rhodium complex catalyzed hydroformylation reactions of linear and cyclic mono- and diolefins
Trzeciak, Anna M.,Ziolkowski, Jozef J.
, p. 213 - 216 (1994)
The hydroformylation reactions of cyclopentene, cyclohexene, 4-vinylcyclohexene, cycloheptene and cyclooctene, catalyzed with a Rh(acac)2/P(OPh)3 (I) system at 80 deg C and 10 atm (CO+H2), have been studied.Only cyclopentene and 4-vinylcyclohexene undergo hydroformylation at 1 atm and 40 deg C.The hydroformylation of some cyclic dienes; (1,3- and 1,4-cyclohexadienes, 1,3- and 1,5-cyclooctadienes and 1,3-cyclopentadiene), at 10 atm and 80 deg C, was investigated in two catalytic systems: (I) and Rh(acac) (CO) (PPh3) / PPh3 (II).The main reaction products of cyclohexadienes and pentadiene (at 80 deg C, 10 atm) are unsaturated monoaldehydes.In hydroformylation of 1,5-cyclooctadiene the main product is formylcyclooctane.Key words: Rhodium; Olefins; Hydroformylation
