502-49-8Relevant academic research and scientific papers
Oxidations of secondary alcohols to ketones using easily recyclable bis(trifluoroacetate) adducts of fluorous alkyl iodides, CF3(CF 2)n-1I(OCOCF3)2
Tesevic, Verona,Gladysz
, p. 7433 - 7440 (2006)
Reactions of commercial fluorous alkyl iodides RfnI (1-R fn; Rfn = CF3(CF2)n-1; n = 7, 8, 10, 12) with 80% H2O2 and trifluoroacetic anhydride give RfnI(OCOC
Manganese Porphyrins Supported on Montmorillonite as Hydrocarbon Mono-oxygenation Catalysts: Particular Efficacy for Linear Alkane Hydroxylation
Barloy, Laurent,Battioni, Pierrette,Mansuy, Daniel
, p. 1365 - 1367 (1990)
A supported Mn-porphyrin catalyst has been prepared by immobilisation of the tetracationic Mn Cl4+ on montmorillonite, and is found to be efficient for alkene epoxidation and alkane hydroxylation by PhIO, with a higher ability to oxidize alkanes, and in particular short linear alkanes, than corresponding homogeneous or silica-supported Mn-porphyrin catalysts.
Metal complexes of a tetraazacyclotetradecane bearing highly fluorinated tails: New catalysts for the oxidation of hydrocarbons under fluorous biphasic conditions
Pozzi, Gianluca,Cavazzini, Marco,Quici, Silvio,Fontana, Simonetta
, p. 7605 - 7608 (1997)
The commercially available macrocycle tetraazacyclotetradecane (cyclam) has been converted into the fluorocarbon soluble ligand 1 by N-functionalization with R(F)CH2OCH2CH2OTs 3, wherein R(F) is a (per)fluorooxyalkylenic c
Nonheme iron mediated oxidation of light alkanes with oxone: Characterization of reactive oxoiron(IV) ligand cation radical intermediates by spectroscopic studies and DFT calculations
Tse, Chun-Wai,Chow, Toby Wai-Shan,Guo, Zhen,Lee, Hung Kay,Huang, Jie-Sheng,Che, Chi-Ming
, p. 798 - 803 (2014)
The oxidation of light alkanes that is catalyzed by heme and nonheme iron enzymes is widely proposed to involve highly reactive {FeViO} species or {FeIViO} ligand cation radicals. The identification of these high-valent iron species and the development of an iron-catalyzed oxidation of light alkanes under mild conditions are of vital importance. Herein, a combination of tridentate and bidentate ligands was used for the generation of highly reactive nonheme {FeiO} species. A method that employs [Fe III(Me3tacn)(Cl-acac)Cl]+ as a catalyst in the presence of oxone was developed for the oxidation of hydrocarbons, including cyclohexane, propane, and ethane (Me3tacn=1,4,7-trimethyl-1,4,7- triazacyclononane; Cl-acac=3-chloro-acetylacetonate). The complex [Fe III(Tp)2]+ and oxone enabled stoichiometric oxidation of propane and ethane. ESI-MS, EPR and UV/Vis spectroscopy, 18O labeling experiments, and DFT studies point to [Fe IV(Me3tacn)({Cl-acac}.+)(O)]2+ as the catalytically active species. Highly reactive {FeiO} intermediates, such as [Fe(Tp)2(O)]+ or complex I (see Scheme), are likely to be involved in the oxidation of propane and ethane with oxone that is either mediated by [FeIII(Tp)2]+ (1) or catalyzed by iron complex 2. The cationic intermediate I features an {FeiO} moiety and is stabilized by a combination of tridentate and bidentate ligands. Copyright
Transition metal-substituted polyoxometalates supported on MCM-41 as catalysts in the oxidation of cyclohexane and cyclooctane with H2O2
Jatupisarnpong, Jirarot,Trakarnpruk, Wimonrat
, p. 152 - 153 (2012)
The Keggin type polyoxometalates (Bu4N)4HPW11CoO39, (Bu4N)4PW11FeO39, (Bu4N)4HPW11CuO39 and (Bu4N)4PW11VO40 have been synthesized and supported on MCM-41 to be used as catalysts for the solvent-free oxidation of cyclohexane and cyclooctane with H2O2.
Alkane hydroxylation by a nonheme iron catalyst that challenges the heme paradigm for oxygenase action
Company, Anna,Gomez, Laura,Gueell, Mireia,Ribas, Xavi,Luis, Josep M.,Que Jr., Lawrence,Costas, Miquel
, p. 15766 - 15767 (2007)
A nonheme iron catalyst catalyzed stereoselective oxidation of alkanes with H2O2 with remarkable efficiency and exhibiting an unprecedented high incorporation of water into the oxidized products. The present results challenge the canonical description of oxygenases, the standard oxo-hydroxo tautomerism that applies to heme systems and serves as a precedent for alternative pathways for the oxidation of hydrocarbons at nonheme iron oxygenases. Copyright
Iron catalysis for in situ regeneration of oxidized cofactors by activation and reduction of molecular oxygen: A synthetic metalloporphyrin as a biomimetic NAD(P)H oxidase
Maid, Harald,Boehm, Philipp,Huber, Stefan M.,Bauer, Walter,Hummel, Werner,Jux, Norbert,Groeger, Harald
, p. 2397 - 2400 (2011)
(Figure Presented) An enzyme substitute: A synthetic FeIII porphyrin was used as a catalyst for the activation and reduction of O 2 into H2O with the cofactor NAD(P)H in aqueous solution. The catalyst is compatible with different preparative enzymatic oxidation reactions. Thus, a new method is provided for the in situ regeneration of the oxidized cofactor NAD(P)+ with help from a nonenzymatic, synthetic catalyst (see scheme).
Reaction of aldehydes with the H5PV2Mo10O40 polyoxometalate and cooxidation of alkanes with molecular oxygen
Khenkin, Alexander M.,Rosenberger, Avi,Neumann, Ronny
, p. 82 - 91 (1999)
The oxidation of alkalies with molecular oxygen using aldehydes as reducing agents (aldehydes are cooxidized) was studied using the α-H5PV2Mo10O40 polyoxometalate as catalyst. Emphasis was placed on the initiation of the radical chain reaction by investigation of the aldehyde-polyoxometalate interaction. Using 31P NMR and ESR spectroscopy one could differentiate between the reactivity of the five inseparable isomers of α-H5PV2Mo10O40. Contrary to previous belief, the 1,11 isomer with vanadium in distal positions is the most abundant. The 31P NMR and ESR spectra supported by UV-vis absorption-time profiles of the reduction of α-H5PV2Mo10O40 indicated that isomers with vanadium in vicinal positions were most kinetically viable in the alkane oxidation. Addition of isobutyraldehyde to α-H5PV2Mo10O40 gave in the 51V NMR spectrum a new downfield peak attributed to the formation of an aldehyde-polyoxometalate intermediate. The alkane/aldehyde/O2 oxidizing system was found to be quite effective and selective for ketone formation. Reaction probes indicated that acyl peroxo radicals were the active oxidizing intermediates. Five pathways for its reaction were identified: chain propagation, alkane oxidation, decomposition to form oxygen, decomposition to acyl oxo radicals leading to CO2 and ketone, and capture and inhibition by the polyoxometalate.
Selective Homogeneous Catalytic Oxidation of Olefins using Oxygen/Hydrogen Mixtures: Oxygen Atom Transfer from an Iridium Hydroperoxide
Atlay, Mark T.,Preece, Michael,Strukul, Giorgio,James, Brian R.
, p. 406 - 407 (1982)
An iridium(III) hydride complex in solution catalyses the O2-co-oxidation of cyclo-octene and H2 to cyclo-octanone and water, respectively, via a hydroperoxide intermediate.
Templating an N-heterocyclic carbene (NHC)-cyclometalated Cp?IrIII-based oxidation precatalyst on a pendant coordination platform: Assessment of the oxidative behavior via electrochemical, spectroscopic and catalytic probes
Gupta, Suraj K.,Choudhury, Joyanta
, p. 1233 - 1239 (2015)
The coordination of metalloligands to derive modified properties of the metal functionality is one of the interesting strategies practiced in materials chemistry and catalysis. In this work, a pendant terpyridine ligand has been utilized for templating a Cp?IrIII(NHC)-based (NHC = N-heterocyclic carbene) oxidation precatalyst to assess its modified oxidative behavior via electrochemical, UV-vis spectroscopic, and catalytic probes. These studies suggested that the coordination-template enhances the electron-deficiency at the IrIII redox center and affects the nature of the oxidized high-valent Ir-oxo species during chemical oxidation. Moreover, both the premodified and postmodified Cp?IrIII(NHC)-based complexes were found to be equally efficient in catalytic sp3 C-H oxidation reactions with NaIO4 as a mild sacrificial oxidant.
