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Hydride Abstraction (hydride + abstraction)
Selected AbstractsMechanism of Hydride Abstraction by Cyclopentadienone-Ligated Carbonylmetal Complexes (M = Ru, Fe)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2009Megan K. Thorson Abstract Cyclopentadienone-ligated ruthenium complexes, such as Shvo's catalyst, are known to oxidize reversibly alcohols to the corresponding carbonyl compounds. The mechanism of this reaction has been the subject of some controversy, but it is generally believed to proceed through concerted transfer of proton and hydride, respectively, to the cyclopentadienone ligand and the ruthenium center. In this paper we further study the hydride transfer process as an example of a coordinatively directed hydride abstraction by adding quantitative understanding to some features of this mechanism that are not well understood. We find that an oxidant as weak as acetone can be used to re-oxidize the intermediate ruthenium hydride without catalyst re-oxidation becoming rate-limiting. Furthermore, C,H cleavage is a significantly electrophilic event, as demonstrated by a Hammett reaction parameter of , = ,0.89. We then describe how the application of our mechanistic insights obtained from the study have enabled us to extend the ligand-directed hydride abstraction strategy to include a rare example of an iron(0) oxidation catalyst.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Cationic Polymerization of 2-Vinylthiophene by Chloroarylmethanes as Surface Initiators on Silica and Consecutive Hydride Abstraction by AcceptorsMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 12 2004Susanne Höhne Abstract Summary: 2-Vinylthiophene (2-VT) has been cationically polymerized using chloroarylmethane derivatives as the surface polymerization initiator on silica. By applying this procedure a soluble fraction of poly(vinylthiophene) (PVT) and PVT/silica composites can be simultaneously synthesized. The mass balance of the products (soluble fraction and hybrid particle fraction) depends significantly on temperature and 2-VT/silica ratio. The hydride abstraction reaction of PVT both in solution and immobilized on silica particle surface has been studied using 2,3-dichloro-5,6-dicyano-1,4-quinone (DDQ), tetrachloro-1,4-quinone (chloranile,=,ClA) and triphenylmethylium as reagents. The transformation process of PVT towards conjugated polymers has been studied with UV-vis spectroscopy and ESR spectroscopy. Cyclic voltammetry shows that chloranil is complexated with the formed polymer. Radical formation increases with increasing degree of conversion. The soluble fraction of the conjugated PVT sections formed is capable of reacting with each other as evidenced by GPC data. Structure of PVT/silica and resulting hybrid materials have been investigated by solid state 13C {1H} CP MAS NMR-spectroscopy showing a reaction of methine and methylene hydrogen atoms after treatment with DDQ or chloranil as hydride acceptors. For all poly-(2-vinylthiophene)/hydride acceptor systems studied, chloranil has been found to be the best reagent for the transformation of PVT towards conjugated polymers. Transformation of PVT in poly(2-ethinylthiophene) (PET) and PVT-PET copolymers. [source] Generation of Cationic [Zr-{tert -Butyl Enolate}] Reactive Species: Methyl Abstraction versus Hydride AbstractionCHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2004Bing Lian Dr. Abstract Treatment of the neutral methyl,Zr,enolate [Cp2Zr(Me){O(tBuO)CCMe2}] (1) with one equivalent of B(C6F5)3 or [HNMe2Ph][B(C6F5)4] as a methyl abstractor in THF at 0,°C leads to the selective formation of the free ion pair complex [Cp2Zr(THF){O(tBuO)CCMe2}]+,[anion], (2) (anion=MeB(C6F5)3,, B(C6F5)4,), which is relevant to the controlled polymerization of methacrylates. Cation 2 rapidly decomposes at 20,°C in THF with release of one equivalent of isobutene to form the cationic Zr,carboxylate species [Cp2Zr(THF)(O2CiPr)]+ (3), through a proposed intramolecular proton transfer process from the tert -butoxy group to the enolate. The reaction of 1 with one equivalent of B(C6F5)3 or [HNMe2Ph][B(C6F5)4] in CH2Cl2 leads to the direct, rapid formation of the dimeric ,-isobutyrato,Zr dicationic species [{Cp2Zr[,-(O2CiPr)]}2]2+ (4), which gives 3 upon dissolution in THF. Contrastingly, when [Ph3C][B(C6F5)4] is used to generate the cationic Zr,enolate species from 1 in CD2Cl2, a 15:85 mixture of dicationic complexes 4 and [{Cp2Zr[, -(O2CC(Me)CH2)]}2]2+[B(C6F5)4] (5 -[B(C6F5)4]2) is obtained quantitatively. The formation of 5 is proposed to arise from initial hydride abstraction from a methyl enolate group by Ph3C+, as supported by the parallel production of Ph3CH, and subsequent elimination of methane and isobutene. In addition to standard spectroscopic and analytical characterizations for the isolated complexes 2,5, complexes 4 and 5 have also been structurally characterized by X-ray diffraction studies. [source] Mechanism of Hydride Abstraction by Cyclopentadienone-Ligated Carbonylmetal Complexes (M = Ru, Fe)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2009Megan K. Thorson Abstract Cyclopentadienone-ligated ruthenium complexes, such as Shvo's catalyst, are known to oxidize reversibly alcohols to the corresponding carbonyl compounds. The mechanism of this reaction has been the subject of some controversy, but it is generally believed to proceed through concerted transfer of proton and hydride, respectively, to the cyclopentadienone ligand and the ruthenium center. In this paper we further study the hydride transfer process as an example of a coordinatively directed hydride abstraction by adding quantitative understanding to some features of this mechanism that are not well understood. We find that an oxidant as weak as acetone can be used to re-oxidize the intermediate ruthenium hydride without catalyst re-oxidation becoming rate-limiting. Furthermore, C,H cleavage is a significantly electrophilic event, as demonstrated by a Hammett reaction parameter of , = ,0.89. We then describe how the application of our mechanistic insights obtained from the study have enabled us to extend the ligand-directed hydride abstraction strategy to include a rare example of an iron(0) oxidation catalyst.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Collision-induced loss of AgH from Ag+ adducts of alkylamines, aminocarboxylic acids and alkyl benzyl ethers leads exclusively to thermodynamically favored product ionsJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 2 2009Mathias Schäfer Abstract The loss of AgH from [M + Ag]+ precursor ions of tertiary amines, aminocarboxylic acids and aryl alkyl ethers is examined by deuterium labeling combined with collision activation (CA) dissociation experiments. It was possible to demonstrate that the AgH loss process is highly selective toward the hydride abstraction. For tertiary amines and aminocarboxylic acids, hydrogen originates from the ,-methylene group carrying the nitrogen function (formation of an immonium ion). In all cases examined, the most stable, i.e. the thermodynamically favored product ion is formed. In the AgH loss process, a large isotope effect operates discriminating against the loss of D. The [M + Ag]+ ion of benzyl methyl ether loses a hydride ion exclusively from the benzylic methylene group supporting the experimental finding that the AgH loss reaction selectively cleaves the weakest CH bond available. Copyright © 2008 John Wiley & Sons, Ltd. [source] Generation of Cationic [Zr-{tert -Butyl Enolate}] Reactive Species: Methyl Abstraction versus Hydride AbstractionCHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2004Bing Lian Dr. Abstract Treatment of the neutral methyl,Zr,enolate [Cp2Zr(Me){O(tBuO)CCMe2}] (1) with one equivalent of B(C6F5)3 or [HNMe2Ph][B(C6F5)4] as a methyl abstractor in THF at 0,°C leads to the selective formation of the free ion pair complex [Cp2Zr(THF){O(tBuO)CCMe2}]+,[anion], (2) (anion=MeB(C6F5)3,, B(C6F5)4,), which is relevant to the controlled polymerization of methacrylates. Cation 2 rapidly decomposes at 20,°C in THF with release of one equivalent of isobutene to form the cationic Zr,carboxylate species [Cp2Zr(THF)(O2CiPr)]+ (3), through a proposed intramolecular proton transfer process from the tert -butoxy group to the enolate. The reaction of 1 with one equivalent of B(C6F5)3 or [HNMe2Ph][B(C6F5)4] in CH2Cl2 leads to the direct, rapid formation of the dimeric ,-isobutyrato,Zr dicationic species [{Cp2Zr[,-(O2CiPr)]}2]2+ (4), which gives 3 upon dissolution in THF. Contrastingly, when [Ph3C][B(C6F5)4] is used to generate the cationic Zr,enolate species from 1 in CD2Cl2, a 15:85 mixture of dicationic complexes 4 and [{Cp2Zr[, -(O2CC(Me)CH2)]}2]2+[B(C6F5)4] (5 -[B(C6F5)4]2) is obtained quantitatively. The formation of 5 is proposed to arise from initial hydride abstraction from a methyl enolate group by Ph3C+, as supported by the parallel production of Ph3CH, and subsequent elimination of methane and isobutene. In addition to standard spectroscopic and analytical characterizations for the isolated complexes 2,5, complexes 4 and 5 have also been structurally characterized by X-ray diffraction studies. [source] | ||||||||||