Добірка наукової літератури з теми "Olefin oxidation"
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Статті в журналах з теми "Olefin oxidation"
Perkins, Robert J., Hai-Chao Xu, John M. Campbell, and Kevin D. Moeller. "Anodic coupling of carboxylic acids to electron-rich double bonds: A surprising non-Kolbe pathway to lactones." Beilstein Journal of Organic Chemistry 9 (August 9, 2013): 1630–36. http://dx.doi.org/10.3762/bjoc.9.186.
Повний текст джерелаRayati, Saeed, Saeed Zakavi, Parisa Jafarzadeh, Omid Sadeghi, and Mostafa M. Amini. "Manganese meso-tetra-4-carboxyphenylporphyrin immobilized on MCM-41 as catalyst for oxidation of olefins with different oxygen donors in stoichiometric conditions." Journal of Porphyrins and Phthalocyanines 16, no. 03 (March 2012): 260–66. http://dx.doi.org/10.1142/s1088424612500307.
Повний текст джерелаLin, Bo-Lin, Jay A. Labinger, and John E. Bercaw. "Mechanistic investigations of bipyrimidine-promoted palladium-catalyzed allylic acetoxylation of olefins." Canadian Journal of Chemistry 87, no. 1 (January 1, 2009): 264–71. http://dx.doi.org/10.1139/v08-133.
Повний текст джерелаKřeček, Václav, Jiří Protiva, Miloš Buděšínský, Eva Klinotová, and Alois Vystrčil. "Preparation of C(18)-empiric 20,29,30-trinorlupane derivatives. 1H, 13C NMR and mass spectra." Collection of Czechoslovak Chemical Communications 51, no. 3 (1986): 621–35. http://dx.doi.org/10.1135/cccc19860621.
Повний текст джерелаSTINSON, STEPHEN. "IRON-CATALYZED OLEFIN OXIDATION." Chemical & Engineering News 79, no. 30 (July 23, 2001): 9. http://dx.doi.org/10.1021/cen-v079n030.p009.
Повний текст джерелаLorber, Christian. "[ONNO]-type amine bis(phenolate)-based vanadium catalysts for ethylene homo- and copolymerization." Pure and Applied Chemistry 81, no. 7 (June 30, 2009): 1205–15. http://dx.doi.org/10.1351/pac-con-08-08-05.
Повний текст джерелаHerrmann, Wolfgang A., Richard W. Fischer, and Dieter W. Marz. "Methyltrioxorhenium as Catalyst for Olefin Oxidation." Angewandte Chemie International Edition in English 30, no. 12 (December 1991): 1638–41. http://dx.doi.org/10.1002/anie.199116381.
Повний текст джерелаFukusumi, Takanori, Natsuki Takei, Yubi Tateno, Takuya Aoki, Ai Ando, Kouhei Kozakai, Hiroko Shima, et al. "Ene-thiol reaction of C3-vinylated chlorophyll derivatives in the presence of oxygen: synthesis of C3-formyl-chlorins under mild conditions." Journal of Porphyrins and Phthalocyanines 17, no. 12 (December 2013): 1188–95. http://dx.doi.org/10.1142/s1088424613500983.
Повний текст джерелаMa, Baochun, Wei Zhao, Fuming Zhang, Yingshuai Zhang, Songyun Wu, and Yong Ding. "A new halide-free efficient reaction-controlled phase-transfer catalyst based on silicotungstate of [(C18H37)2(CH3)2N]3[SiO4H(WO5)3] for olefin epoxidation, oxidation of sulfides and alcohols with hydrogen peroxide." RSC Adv. 4, no. 61 (2014): 32054–62. http://dx.doi.org/10.1039/c4ra04036h.
Повний текст джерелаPatrzałek, Michał, Aleksandra Zasada, Anna Kajetanowicz та Karol Grela. "Tandem Olefin Metathesis/α-Ketohydroxylation Revisited". Catalysts 11, № 6 (9 червня 2021): 719. http://dx.doi.org/10.3390/catal11060719.
Повний текст джерелаДисертації з теми "Olefin oxidation"
Javadekar, Ashay Dileep. "Surface science studies of olefin oxidation on the silver surface." Access to citation, abstract and download form provided by ProQuest Information and Learning Company; downloadable PDF file, 131 p, 2009. http://proquest.umi.com/pqdweb?did=1889838931&sid=2&Fmt=2&clientId=8331&RQT=309&VName=PQD.
Повний текст джерелаHamidi, A. "Interaction between hindered piperidine light stabilisers and antioxidants in the thermal and photochemical oxidation of polyolefins." Thesis, Manchester Metropolitan University, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.378064.
Повний текст джерелаTownsend, Erik Matthew. "High-oxidation-state molybdenum and tungsten monoalkoxide pyrrolide alkylidenes as catalysts for olefin metathesis." Thesis, Massachusetts Institute of Technology, 2014. http://hdl.handle.net/1721.1/91116.
Повний текст джерелаCataloged from PDF version of thesis. Vita.
Includes bibliographical references.
Chapter 1 describes work toward solid-supported W olefin metathesis catalysts. Attempts to tether derivatives of the known Z-selective catalyst W(NAr)(C₃H₆)(pyr)(OHIPT) (Ar = 2,6- diisopropylphenyl, pyr = pyrrolide; HIPT = 2,6-bis-(2,4,6-triisopropylphenyl)phenyl) to a modified silica surface by covalent linkages are unsuccessful due to destructive interactions between W precursors and silica. W(NAr)(C₃H₆)(pyr)(OHIPT) and W(NAr)(CHCMe₂Ph)(pyr)(OHIPT-NMe₂) (HIPT-NMe 2 = 2,6-bis-(2,4,6-triisopropylphenyl)-4- dimethylaminophenyl) are adsorbed onto calcined alumina. W(NAr)(C 3H6 )(pyr)(OHIPT) is destroyed upon binding to alumina, while W(NAr)(CHCMe 2Ph)(pyr)(OHIPT-NMe 2) appears to bind through a non-destructive interaction between the dimethylamino group and an acidic surface site. The heterogeneous catalysts perform non-stereoselective metathesis of terminal olefins, and W(NAr)(CHCMe₂Ph)(pyr)(OHIPT-NMe₂) can be washed off the surface with polar solvent and perform solution-phase Z-selective metathesis. Chapter 2 details selective metathesis homocoupling of 1,3-dienes with Mo and W monoalkoxide pyrrolide (MAP) catalysts. A catalytically relevant vinylalkylidene complex, Mo(NAr)(CHCHCH(CH₃)₂)(Me₂pyr)(OHMT) (HMT = 2,6-bis(2,4,6-trimethylphenyl)phenyl; Me₂pyr = 2,5-dimethylpyrrolide), is isolated. A series of Mo and W MAP catalysts is synthesized and tested for activity, stereoselectivity, and chemoselectivity in 1,3-diene metathesis homocoupling. Catalysts containing the OHIPT ligand display excellent selectivity in general, and W catalysts are less active but more selective than their Mo counterparts. Chapter 3 recounts the synthesis and characterization of several heteroatom-substituted alkylidene complexes with the formula Mo(NAr)(CHER)(Me₂pyr)(OTPP) (TPP = 2,3,5,6- tetraphenylphenyl; ER = OPr, N-pyrrolidinonyl, N-carbazolyl, pinacolborato, trimethylsilyl, SPh, or PPh2). Synthesis proceeds via alkylidene exchange between Mo(NAr)(CHR)(Me₂pyr)(OTPP) (R = H, CMe₂Ph) and a CH₂CHER precursor. Each complex behaves similarly to known MAP complexes in olefin metathesis processes; the electronic identity of ER has little effect on catalytic properties. Distinctive features of alkylidene isomerism and catalyst resting state are examined. Chapter 4 contains synthetic and catalytic studies of thiolate-containing Mo and W imido alkylidene complexes. The species M(NAr)(CHCMe 2Ph)(pyr)(SHMT) (M = Mo or W), Mo(NAr)(CHCMe₂Ph)(Me₂pyr)(STPP), and Mo(NAr)(CHCMe₂Ph)(STPP)₂ are synthesized by substitution of the appropriate thiol or thiolate ligands for pyrrolide or triflate ligands in metal precursors. These complexes show similar structural and spectral characteristics to alkoxidecontaining species. The thiolate complexes and their alkoxide analogues are compared for activity and selectivity in metathesis homocoupling and ring-opening metathesis polymerization processes. In general, thiolate catalysts are slower and less selective than alkoxide catalysts.
by Erik Matthew Townsend.
Ph. D.
Flook, Margaret McGuigan. "Z-selective olefin metathesis processes and Cis/syndioselective ROMP with high oxidation state molybdenum alkylidenes." Thesis, Massachusetts Institute of Technology, 2012. http://hdl.handle.net/1721.1/73354.
Повний текст джерелаVita. Cataloged from PDF version of thesis.
Includes bibliographical references.
Chapter 1: Reaction of W(CCMe3)Cl 3(dme) with one equivalent of (3,5-Me 2C6H3NCH2CH 2)3N)Li3 affords yellow, crystalline W(CCMe3)(N3N) in good yield. The reactivity of this new alkylidyne complex towards terminal alkynes was investigated. Two other new tungsten alkylidynes, W(CCMe3)(pyr) 3 (pyr = 2,5-dimethylpyrrolide) and W(CCMe3)(Ph 2N)3 were prepared by the addition of three equivalents of lithium dimethylpyrrolide or lithium diphenylamide, respectively, to W(CCMe3)Cl 3(dme). The reactivity of these new alkylidynes with various alcohols is reported. The reactivity of several tungsten alkylidyne compounds towards ligand displacement by surface silanols is reported, resulting in the synthesis of several new silicasupported tungsten alkylidynes. The alkyne metathesis activity of all new homogeneous and heterogeneous alkylidyne complexes is reported. Chapter 2: Addition of one equivalent of 2,4,6,2',4',6'-hexaisopropylterphenol to Mo(NAd)(CHCMe 2Ph)(pyr)2 results in the formation of Mo(NAd)(CHCMe 2Ph)(pyr)(HIPTO) (HIPTO = hexaisopropylterphenoxide). This new alkylidene compound was found to catalyze the metathesis of 1-hexene in 20% yield to 95% cis 5-decene, which represents the first report of highly Z-selective metathesis homocoupling of a terminal olefin. The decomposition of the catalyst in the presence of ethylene is explored. The syntheses of several new bulky achiral phenoxide ligands are presented, along with the syntheses of the corresponding MAP (monoalkoxide monopyrrolide) molybdenum imido alkylidene compounds. The reactivity of new MAP compounds containing bulky phenoxide ligands towards the Z-selective metathesis of terminal and internal olefins is presented. The cis-selectivity of this system is proposed to arise from the combination of a relatively small imido ligand in conjunction with a very bulky alkoxide forcing the substituents of the substrate to point in this same direction with each insertion. Photolysis of MAP compounds with 366 nm radiation was found to produce significant amounts of anti alkylidenes, and the kinetics of decay of unstable anti alkylidenes are investigated. Chapter 3: The reaction of 2,3-dicarbomethoxynorbomadiene (DCMNBD) with Mo(NAd)(CHCMe 2Ph)(pyr)(HIPTO) (Ad = 1-adamantyl, HIPTO = hexaisopropylterphenoxide) affords >98% cis, >98% tactic polyDCMNBD. The tacticity of this polymer is proved to be syndiotactic through polymerization of DCMenthNBD (2,3-dicarbomenthoxynorbomadiene) and IH- H COSY. A variety of related MAP alkylidene compounds are also investigated towards the ROMP of DCMNBD and found to produce polyDCMNBD in a range of tacticities and cis contents. Highly cis polyNBDF6 (poly-bis(CF 3)-norbomadiene) was also prepared using molybdenum MAP compounds, and the resulting polymer was found to be essentially insoluble in common organic solvents. Solid state CPMAS 13C NMR spectroscopy revealed insoluble polyNBDF6 to be highly tactic, and the tacticity is proposed to be syndiotactic. Cis, tactic polymer was prepared through the addition of 3,3-methylphenylcyclopropene (MPCP) to molybdenum MAP compounds. Attempts towards determination of the tacticity of cispolyMPCP are presented, including the synthesis of three 3,3-disubstituted cyclopropene monomers containing chiral tags. The cis-selective ROMP of cyclooctene and 1,5- cyclooctadiene are reported. The syndioselectivity of the catalysts is proposed to be controlled by the configuration of the 4-coordinate metal center, which alternates with each insertion of monomer. Chapter 4: Racemic 2,3-dicarbomethoxynorbornene (rac-DCMNBE) is polymerized by Mo(NAd)(CHCMe 2Ph)(pyr)(HMTO) (Ad = 1-adamantyl, pyr = pyrrolide, HMTO = hexamethylterphenoxide) to afford an all-cis polymer that is syndiotactic and composed of alternating enantiomers. The cis, syndiotactic ROMP of several other racemic chiral monomers are reported, also affording structures containing a high degree of enantiomer alteration. Attempts towards the alternating copolymerization of two different monomers are reported. The ROMP of enantiomerically pure (+)-dicarbomethoxynorbornene with Mo(NAd)(CHCMe 2Ph)(pyr)(HIPTO) leads to the production of 92% trans-isotactic polyDCMNBE. The structure of trans-isotactic polyDCMNBD is proved through hydrogenation and comparison of its 3C NMR spectrum with that of known cis-isotactic polyDCMNBE. Both cis/syndiotactic/alternating poly-rac-DCMNBE and trans/isotactic poly-(+)-DCMNBE are polymer structures that have not been previously reported. The thermal properties of all new polymers and their hydrogenated counterparts are reported and are found to correlate closely with polymer structure.
by Margaret McGuigan Flook.
Ph.D.
Ackerman, Lily Joy Grubbs Robert H. Bercaw John E. "Ancillary ligand effects in niobocene olefin hydride complexes and hydrocarbon oxidation by palladium(II) complexes /." Diss., Pasadena, Calif. : California Institute of Technology, 2003. http://resolver.caltech.edu/CaltechETD:etd-05212003-130334.
Повний текст джерелаGardan, Martino. "Innovative catalytic processes for oxidation reactions." Doctoral thesis, Università degli studi di Padova, 2009. http://hdl.handle.net/11577/3426141.
Повний текст джерелаLo studio e lo sviluppo di sistemi metallo-catalizzati innovativi per l’ossidazione di molecole organiche con ossidanti sostenibili, specialmente ossigeno molecolare, O2, o acqua ossigenata, H2O2, è una prospettiva di grande attrazione per l’Industria Chimica. Nel progetto di Tesi di Dottorato, sono state sviluppate diverse strategie allo scopo di effettuare trasformazioni ossidative di riferimento quali l’autoossidazione di derivati benzilici, l’idrossilazione di idrocarburi aromatici e l’epossidazione di olefine. In tutti i casi, l’approccio alla ricerca si è basato su alcuni aspetti chiave che prevedono l’utilizzo integrato di: i) ossidanti a basso impatto ambientale quali O2 e H2O2; ii) catalizzatori multi-metallici ad elevata resistenza termica, idrolitica ed ossidativa; iii) tecniche di catalisi eterogenea per mezzo di materiali funzionali ibridi organici-inorganici costituiti da membrane catalitiche a matrice polimerica e protocolli che non prevedano l’impiego di solventi organici; iv) microonde o radiazioni fotochimiche quali tecniche di attivazione non convenzionali; v) tecniche di catalisi multipla con processi sequenziali e/o paralleli (Tandem Catalisi). I catalizzatori impiegati appartengono alla classe degli ossidi polianionici metallici, detti poliossometallati (POMs), aventi formula generale [XxMmOy]q-, dove M è il componente metallico principale (Mo, V, W) e X è un eventuale eteroatomo (P o Si). Questi complessi sono molto vantaggiosi come catalizzatori perché di natura inorganica, resistenti e sono modulabili in termini di struttura, composizione chimica, densità elettronica e carica polianionica. Particolarmente interessante è la possibilità di funzionalizzare la porzione inorganica con domìni di natura organica, potendo così ottenere catalizzatori ibridi organici-inorganici dalle prestazioni catalitiche migliori. Poiché le fasi fluorurate sono di particolare interesse per ciò che concerne le trasformazioni ossidative, l’attività di ricerca si è focalizzata sulla sintesi, caratterizzazione e attività catalitica di nuovi poliossometallati fluorurati. Sono state seguite due strategie di sintesi differenti basate sulla metatesi di controcatione e sulla funzionalizzazione covalente di superfici di POM inorganici. Con la prima strategia è stato isolato il polianione decatungstato (W10O32)4- con un controcatione tetraalchilammonio fluorurato ottenedo il sale fluorofilico ?[CF3(CF2)7(CH2)3]3CH3N}4W10O32 , (RfN4W10). Il decatungstato è noto per la sua capacità di essere iniziatore di processi radicalici se fotoirradiato in atmosfera di ossigeno. L’ossidazione fotocatalitica di etilbenzene ed altri idrocarburi benzilici tramite RfN4W10 e O2 è stata condotta in 1,1,1,3,3,3-hexafluoroisopropanolo (HFIP), sia in omogeneo che in fase eterogenea. L’applicazione della tecnologia delle membrane per la catalisi eterogenea offre, in particolare, numerosi vantaggi in termini di combinazioni di avanzati processi di separazione molecolare con proprietà di trasporto selettive, insieme alla reattività su supporti solidi. L’eterogeneizzazione del fotocatalizzatore è stata così ottenuta per incorporazione di RfN4W10 in film polimerici perfluorurati di HYFLON AD 60X, ottenendo così nuovi materiali ibridi da impiegare e reciclare in processi “multi-turnover” ed in assenza di solventi. Immagini di microscopia elettronica a scansione (SEM) della superficie e della sezione del film evidenziano una distribuzione omogenea ed altamente dispersa dei domini catalitici che appaiono come particelle sferiche a dimensioni uniformi e di diametro pari a circa 2-3 ?m. Inoltre, in condizioni controllate, è stato possibile ottenere una membrana porosa da poter utilizzare in un reattore a flusso continuo. Nelle condizioni testate, la fotoossigenazione con (RfN)4W10O32 dà benzilidroperossido ed il corrispondente alcool e chetone. E’importante evidenziare come la fotoossigenazione di tetralina ed indano proceda con TON>6000 e con una elevata selettività in alcool, fornendo così un’ importante alternativa ad altri sistemi di ossigenazione basati su meccanismi di tipo radicalico. Poliossometallati fluorurati sono stati sintetizzati anche tramite l’approccio di funzionalizzazione covalente. Questa strategia prevede l’impiego di poliossotungstati lacunari e organosilil cloruri CF3(CF2)7CH2CH2SiCl3 (RfSiCl3) a dare derivati ibridi per mezzo dell’attacco covalente dei gruppi organici sulla superficie del POM. I complessi finali risultanti, con formula generale Q4[(RfSi)xOySiWwOz], isolati come sali di tetrabutilammonio (Q+) sono stati caratterizzati ed impiegati come catalizzatori per l’epossidazione di diverse olefine in presenza di H2O2. Studi cinetici e meccanicistici hanno fornito diverse indicazioni circa l’esistenza di un effetto sinergico fra i catalizzatori e il solvente per fluorurato utilizzato (HFIP). E’importante sottolineare come questa reazione attivata da microonde produca epossido in rese quantitative dopo soli 20 minuti anche per le olefine terminali. Ulteriori aspetti trattati riguardano le caratteristiche auto-assemblanti di questi complessi fluorurati anfifilici. Fenomeni di aggregazione in soluzione di HFIP sono stati studiati tramite DLS e tramite microscopia elettronica allo stato solido. Anche l’eterogeneizzazione di questo sistema è stata ottenuta tramite l’approccio di funzionalizzazione covalente. In questo caso, il poliossotungstato lacunare è stato fatto reagire con un silano che porta una catena alchilica insatura terminale: CH2=CH(CH2)6SiCl3 (RSiCl3). La morfologia e la struttura del materiale ibrido risultante sono state modulate attraverso la variazione del rapporto dei solventi porogenici e dei comonomeri impiegati nella miscela di polimerizzazione. Il polimero ibrido finale presenta l’interessante proprietà di rigonfiare in alcool fluorurati, dove l’epossidazione di cis-cicloottene avviene con rese quantitative in 15 minuti. Infine, è stato studiato il processo POM-catalizzato per la sintesi di fenolo: uno degli intermedi e commodity a più alto valore di mercato. A questo scopo l’attività di ricerca è stata incentrata sullo studio sia del processo autoossidativo, sia della mono-idrossilazione diretta del benzene. (i) L’applicazione di tecniche di Tandem Catalisi, allo scopo di sfruttare la produzione con sistema a membrana foto catalitica del cumilidroperossido da cumene, e promuoverne la sua decomposizione a fenolo in un secondo stadio con un catalizzatore POM-acido, (ii) lo screening di diversi molibdovanadati come catalizzatori da usare con H2O2 per l’idrossilazione di benzene. Nel primo caso, la Tandem Catalisi permette di ottenere una resa in fenolo pari a 63% rispetto alle moli iniziali di cumilidroperossido, nel secondo caso, con H4Mo11VO40 si ha un miglioramento dei dati di letteratura per ottimizzazione della reazione con 17% di conversione, selettività = 90% e TOF = 22.5 h-1.
Shrestha, Sweta. "Application of Transition Metal Coordination for Energy Efficient Processes: Catalysis and Separation." The Ohio State University, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=osu1502975499629018.
Повний текст джерелаAxtell, Jonathan Clayton. "Synthesis and reactivity of high oxidation state tungsten and molybdenum olefin metathesis catalysts bearing new imido ligands." Thesis, Massachusetts Institute of Technology, 2015. http://hdl.handle.net/1721.1/98598.
Повний текст джерелаCataloged from PDF version of thesis.
Includes bibliographical references.
Chapter 1 details the synthesis of tungsten imidoalkylidene compounds bearing strongly electron-withdrawing imido ligands. An alternative synthesis involving the treatment of WCl6 with 4 equivalents of N-trimethylsilyl-substituted anilines and subsequent workup with 1,2-dimethoxyethane (DME) has been employed to form complexes of the type W(NAr)2C12(dme); syntheses employing WO2C 2(dme) as the tungsten precursor were unsuccessful. Alkylation with neopentylmagnesium chloride (ClMgNp) and subsequent treatment with trifluoromethanesulfonic acid (HOTf) affords imidoalkylidene species W(NAr)(CHCMe 3)(OTf)2(dme) (OTf = trifluoromethanesulfonate); analogous neophylidene ([W]CHCMe 2Ph) species could not be made under these conditions. Treatment of these compounds with two equivalents of LiO(2,6-(CHCPh 2)C6H3)-Et2O affords the bisaryloxide complexes of the type W(NAr)(CHCMe3)(OR)2. Ring-Opening Metathesis Polymerization (ROMP) studies using a series of these bisaryloxides show that rates of ROMP increase as the electron-withdrawing power of the substituents on the imido ligand increase if steric bulk about the metal center is held constant. A similar trend between two bisaryloxides is observed for anti-to-syn alkylidene rotation rates at 50*C in toluene-d8 . Difficulties synthesizing bis-pyrrolide complexes of the type W(NAr)(CHCMe3)(pyr)2 precluded their use as catalyst precursors; some MAP species containing the more sterically encumbering 2,5-dimethylpyrrolide ligand are presented and the metathesis activity of MAP species bearing the 2,5-dimethylpyrrolide ligand is discussed. Chapter 2 introduces Mo and W complexes bearing the current extreme in sterically bulky imido ligands, the NHIPT (HIPT = 2,6-(2,4,6-iPr 3CH2)CH3) ligand, in an effort to generate all anti alkylidene species. A non-traditional synthetic route is employed in order to install this ligand first as an anilide, and after subsequent proton transfer, as an imido ligand to form a mixed imido species of the type M(NHIPT)(N'Bu)(NH'Bu)Cl. Addition of one equivalent of 2,6-lutidinium chloride, followed by alkylation affords dialkyl species M(NHIPT)(N'Bu)Np 2, and treatment with three equivalents of pyridinium chloride yields all anti imidoalkylidene dichloride species as mono-pyridine adducts, M(NHIPT)(CHCMe 3)C 2(py) (M = Mo, W). General reactivity, including strategies for removal of the pyridine adduct as well as substitution and metathesis chemistry, are discussed. ROMP of MPCP (MPCP = 3-methyl-3-phenylcyclopropene) by a Mo-based MAP species bearing the NHIPT ligand yields predominantly cis,syndiotactic poly(MPCP) and in the homo-metathesis of 1 -octene yields ~81% cis-7-tetradecene. The possible source of trans olefinic product is addressed. Chapter 3 presents the synthesis of the first (1-adamantyl)imido species of tungsten. The functional equivalent of common bisimido precursors for other Mo/W alkylidene species, [W(NAd) 2C 2(AdNH2)1 2, is shown to be a dimer stabilized by hydrogen-bonding interactions between adamantylamine protons and adjacent chlorides bound to the second metal of the dimer. Subsequent alkylation with ClMgNp affords the expected dialkyl species, and treatment with three equivalents of 3,5-lutidinium chloride affords imidoalkylidene complex W(NAd)(CHCMe 3)(C) 2(lut)2 (lut = 3,5-dimethylpyridine). The most desirable synthetic route toward monoalkoxide pyrrolide (MAP) species proceeds through a monoaryloxide monochloride intermediate W(NAd)(CHCMe 3)(Cl)(OAr)(lut) (Ar = 2,6-(2,4,6-Me 3)C6H3, 2,6-(2,4,6-'Pr 3)C6H3). Removal of lutidine with B(C6 F5 )3 and subsequent treatment with lithium pyrrolide affords W(NAd)(CHCMe3)(pyr)(OAr) (pyr = pyrrolide); 2,5-dimethylpyrrolide analogues (W(NAd)(CHCMe3)(Me2pyr)(OAr) can be accessed via protonolysis by HOAr from W(NAd)(CHCMe3)(Me2pyr)2(lut).
by Jonathan Clayton Axtell.
Ph. D.
Tsang, W. C. Peter 1975. "High oxidation state molybdenum and tungsten imido alkylidene and metallacycle chemistry : catalytic asymmetric olefin metathesis and mechanistic investigation." Thesis, Massachusetts Institute of Technology, 2004. http://hdl.handle.net/1721.1/30064.
Повний текст джерелаVita.
Includes bibliographical references.
Enantiomerically pure molybdenum imido alkylidene complexes of the type Mo(NAr)(CHCMe₂Ph)[Ar'](THF), which contained 3,3'-diaryl (Ar' = Mes (21), Ph (22)) substituted binaphtholate ligands, were prepared and structurally characterized. Complex 21 was a trigonal bipyramidal anti alkylidene complex; both 21 and 22 were anti-THF adducts. Temperature and concentration dependent enantioselective desymmetrization of prochiral trienes by catalyst 21 afforded five- and six-membered heterocycles in >90% conversion and >90% ee. Consumption of the six-membered substrate followed pseudo first-order kinetics. The new catalyst was compatible with a variety of common functional groups. The longevity of the catalysts depended on the concentration of ethylene in solution. The resting state of the catalytic cycle, unsubstituted molybdacyclobutane 70, slowly decomposed to yield propylene. This observation suggests that β-hydride elimination can compete with bimolecular coupling of methylene complexes under some conditions. Chapter 2: Racemic and enantiomerically pure tungsten imido alkylidene complexes, W(NAr)-(CHCMe₂Ph)(Biphen) (23a, Ar = 2,6-i-Pr₂C₆H₃) and W(NAr')(CHCMe₂Ph)(Biphen) (23b, Ar' = 2,6-Me₂C₆H₃) were prepared and shown to be viable catalysts for representative asymmetric ring- closing metathesis reactions. Both catalysts were compatible with a variety of common functional groups. Intermediate tungstacyclobutane complexes were observed when a stoichiometric amount of desymmetrization substrate 62 was added to 23a. The final stable complex 78, formed between the ring-closed product and a tungsten methylene complex, was structurally characterized. Isotopic labeling experiments with ¹³C₂H₄ allowed the observation of
(cont.) unsubstituted tungstacyclobutane complexes (82), ethylene complexes (84), tungstacyclopentane complexes (86), and a heterochiral methylene dimer (85a). The tungstacyclopentane complexes catalyzed slow dimerization of ethylene to 1-butene. The observation of the methylene dimer provides the first direct evidence of a bimolecular decomposition pathway for methylene complexes. Chapter 3 Racemic and enantiomerically pure molybdenum alkylimido alkylidene complexes, Mo(NAd)(CHCMe₂Ph)(Biphen) (19d, Ad = 1-adamantyl) and Mo(NAd)(CHCMe₂Ph)[Trip]-(THF) (20d) were prepared and structurally characterized. Complex 19d was observed almost exclusively as a syn alkylidene isomer, in contrast with 20d which was observed almost exclusively as an anti-THF adduct. Complexes 19d and 20d are the only reported chiral alkylimido alkylidene complexes for enantioselective olefin metathesis reactions. Complex 19d is the first crystallographically characterized four-coordinate adamantylimido alkylidene complex in its base-free form. It offers unique reactivity and selectivity profiles in tandem AROM/RCM and AROM/CM reactions. Complex 19d is compatible with a variety of common functional groups, including boron-containing reagents. Van't Hoff analyses suggest that the bias toward syn-19d isomer is entropy-driven. Chapter 4: Solvent- and base-free molybdenum methylene complexes, Mo(NAr)(Biphen)(CH₂) (114a, Ar = 2,6-i-Pr₂C₆H₃) and Mo(NAd)(Biphen)(CH₂) (114d, Ad = 1-adamantyl) ...
by W.C. Peter Tsang.
Ph.D.
Sen, Suman [Verfasser], and Michael R. [Akademischer Betreuer] Buchmeiser. "High oxidation state N-heterocyclic carbene molybdenum alkylidene complexes : functional-group tolerant olefin metathesis catalysts / Suman Sen ; Betreuer: Michael R. Buchmeiser." Stuttgart : Universitätsbibliothek der Universität Stuttgart, 2016. http://d-nb.info/1118371305/34.
Повний текст джерелаКниги з теми "Olefin oxidation"
Lundin, Angelica. Quantum chemical studies of olefin epoxidation and benzyne biradicals. Göteborg, Sweden: Göteborg University, Faculty of Science, 2007.
Знайти повний текст джерелаVolodymyrovych, Kucher Roman, та Instytut heolohiï i heokhimiï hori͡u︡chykh kopalyn (Akademii͡a︡ nauk Ukraïnsʹkoï RSR), ред. Zhidkofaznoe okislenie nepredelʹnykh soedineniĭ v okisi olefinov. Kiev: Nauk. dumka, 1986.
Знайти повний текст джерелаEndinkeau, Kuang. Oxidative and nonoxidative effects of ionising radiation on palm olein. Salford: University of Salford, 1988.
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Знайти повний текст джерелаЧастини книг з теми "Olefin oxidation"
Novak, B. M., W. Risse, and R. H. Grubbs. "The development of well-defined catalysts for ring-opening olefin metathesis polymerizations (ROMP)." In Polymer Synthesis Oxidation Processes, 47–72. Berlin, Heidelberg: Springer Berlin Heidelberg, 1992. http://dx.doi.org/10.1007/3-540-55090-9_2.
Повний текст джерелаGrate, John H., David R. Hamm, and Suresh Mahajan. "Palladium and Phosphomolybdovanadate Catalyzed Olefin Oxidation to Carbonyls." In Topics in Molecular Organization and Engineering, 281–305. Dordrecht: Springer Netherlands, 1994. http://dx.doi.org/10.1007/978-94-011-0920-8_21.
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Повний текст джерелаSchrock, Richard R. "High-Oxidation State Molybdenum and Tungsten Complexes Relevant to Olefin Metathesis." In Handbook of Metathesis, 1–32. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA, 2015. http://dx.doi.org/10.1002/9783527674107.ch1.
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Повний текст джерелаWeber, S., J. C. W. Chien, and Y. Hu. "Determination of the Titanium Oxidation States in a MgCl2-Supported Ziegler-Natta Catalyst (CW-Catalyst) During Aging and Polymerization." In Transition Metals and Organometallics as Catalysts for Olefin Polymerization, 45–53. Berlin, Heidelberg: Springer Berlin Heidelberg, 1988. http://dx.doi.org/10.1007/978-3-642-83276-5_5.
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Повний текст джерелаShi, Yian. "Organocatalytic Oxidation. Ketone-Catalyzed Asymmetric Epoxidation of Olefins." In Modern Oxidation Methods, 51–82. Weinheim, FRG: Wiley-VCH Verlag GmbH & Co. KGaA, 2005. http://dx.doi.org/10.1002/3527603689.ch3.
Повний текст джерелаТези доповідей конференцій з теми "Olefin oxidation"
Cheenkachorn, Kraipat, Wallis A. Lloyd, and Joseph M. Perez. "Use of Pressurized Differential Scanning Calorimetry (PDSC) to Evaluate Effectiveness of Additives in Vegetable Oil Lubricants." In ASME 2003 Internal Combustion Engine Division Spring Technical Conference. ASMEDC, 2003. http://dx.doi.org/10.1115/ices2003-0657.
Повний текст джерелаZhang, Yi, Yan Luo, Jian-Qiang Hu, Tao Zhang, and Yun-Yun Xu. "Study on Antioxidation Properties of the Complex of Dithiocarbamate With Tolutriazole Antioxidant." In ASME/STLE 2007 International Joint Tribology Conference. ASMEDC, 2007. http://dx.doi.org/10.1115/ijtc2007-44020.
Повний текст джерелаPlechovich, Sergei, Sergei Zelentsov, and Alexandre Plechovich. "Quantum chemical studies of the olefin oxidation in the singlet and triplet states." In The 15th International Electronic Conference on Synthetic Organic Chemistry. Basel, Switzerland: MDPI, 2011. http://dx.doi.org/10.3390/ecsoc-15-00608.
Повний текст джерелаPlehovitch, Sergey, Yuri Minasyan, and Sergei Zelentsov. "Quantum chemical modeling of the olefin oxidation in the triplet state." In The 19th International Electronic Conference on Synthetic Organic Chemistry. Basel, Switzerland: MDPI, 2015. http://dx.doi.org/10.3390/ecsoc-19-e006.
Повний текст джерелаHu, Xiao Li, and Hui Dong Wang. "Study on the Effect of Hydrogenated Lubricant Base Oil Composition to Its Oxidation Stability." In World Tribology Congress III. ASMEDC, 2005. http://dx.doi.org/10.1115/wtc2005-64133.
Повний текст джерелаBerry, David A., Dushyant Shekhawat, Todd H. Gardner, Maria Salazar, Daniel J. Haynes, and James J. Spivey. "Support Effects for Pt and Rh-Based Catalysts for Partial Oxidation of n-Tetradecane." In ASME 2006 4th International Conference on Fuel Cell Science, Engineering and Technology. ASMEDC, 2006. http://dx.doi.org/10.1115/fuelcell2006-97265.
Повний текст джерелаMinasyan, Yuri, Sergey Zelentsov, and Sergey Plehovitch. "Quantum chemical modeling of the olefin oxidation by aromatic nitrocompounds in the triplet state." In The 20th International Electronic Conference on Synthetic Organic Chemistry. Basel, Switzerland: MDPI, 2016. http://dx.doi.org/10.3390/ecsoc-20-e017.
Повний текст джерелаHu, Jian-Qiang, Xian-Jun Zeng, Wei Zhang, and Ben-Ke Shang. "The Synergistic Antioxidation Effects of Molybdenum Dialkydithiocarbamate With Arylamine Antioxidants." In STLE/ASME 2008 International Joint Tribology Conference. ASMEDC, 2008. http://dx.doi.org/10.1115/ijtc2008-71033.
Повний текст джерелаMunoz, Juan Fernando. "High oleic palm oil: Uses and applications." In 2022 AOCS Annual Meeting & Expo. American Oil Chemists' Society (AOCS), 2022. http://dx.doi.org/10.21748/eoga3312.
Повний текст джерелаRadovanović, Mirjana, Dalibor Tomić, Vesna Đurović, Miloš Marjanović, Radmila Ilić та Vera Katanić. "HLADNO PRESOVANА ULJA TIKVE I ORAHA". У XXVII savetovanje o biotehnologiji. University of Kragujevac, Faculty of Agronomy, 2022. http://dx.doi.org/10.46793/sbt27.515r.
Повний текст джерелаЗвіти організацій з теми "Olefin oxidation"
Wayland, B. B. Final Technical Report "Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation" Grant number : DE-FG02-86ER13615. Office of Scientific and Technical Information (OSTI), August 2009. http://dx.doi.org/10.2172/946685.
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