768-95-6Relevant articles and documents
Thermochemistry of Bridged-ring Substances. Enthalpies of Formation of Diamantan-1-, -3-, and -4-ol and of Diamantanone
Clark, Timothy,Knox, Trevor McO.,McKervey, M. Anthony,Mackle, Henry
, p. 1686 - 1689 (1980)
The enthalpies of combustion and of sublimation four mono-oxygenated diamantanes have been determined.The derived solid and gas-phase enthalpies of formation in kcal mol-1 at 298.15 K follow: diamantanone, -81.16+/-0.38, -56.53+/-0.41; diamantan-1-ol, -102.49+/-0.24, -74.30+/-0.28; diamantan-3-ol, -98.89+/-0.35, -71.14+/-1.10; diamantan-4-ol, -103.96+/-0.39, -75.80+/-0.39.Oxo and hydroxy group increments within the diamantane, adamantane, and cyclohexane series are discussed.Enthalpy differences betveen the isomeric diamantanols are compared with existing data from equilibration studies in solution.Comparisons are made between the experimental gas-phase enthalpies of formation and those obtained by molecular mechanics (empirical force field) calculations based on the Allinger MM1 force field model.
Regioselective intramolecular oxidation of unactivated C-H bonds by dioxiranes generated in situ
Yang,Wong,Wang,Tang
, p. 6611 - 6612 (1998)
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Site-isolated porphyrin catalysts in imprinted polymers
Burri, Estelle,Oehm, Margarita,Daguenet, Corinne,Severin, Kay
, p. 5055 - 5061 (2005)
A meso-tetraaryl ruthenium porphyrin complex having four polymerizable vinylbenzoxy groups (2) has been synthesized by reaction of pyrrole with 4-(vinylbenzoxy)benzaldehyde and subsequent metalation with [Ru 3(CO)12]. The porphyrin complex was immobilized by copolymerization with ethylene glycol dimethacrylate. The resulting polymer P2 was found to catalyze the oxidation of alcohols and alkanes with 2,6-dichloropyridine N-oxide without activation by mineral acids. Under similar conditions, the homogeneous catalyst 2 was completely inefficient. By using diphenylaminomethane and 1-aminoadamantane as coordinatively bound templates during the polymerization procedure, the molecularly imprinted polymers P3 and P4 have been synthesized. Compared with the polymer P2, the imprinted catalysts displayed a significantly increased activity with rate enhancements of up to a factor of 16.
Schleyer,Nicholas
, p. 2700,2706 (1961)
Schleyer et al.
, p. 4195 (1964)
Foiled conjugation in α-oximino carbocations
Creary, Xavier,Jiang, Ziqi
, p. 3482 - 3489 (1996)
The 4-CHNOCH3 group is a cation-stabilizing group when placed in the para-position of a cumyl cation. The effect of this group on cumyl cations when flanked by adjacent methyl groups has now been determined. Solvolysis rates of 3,5-(CH3)2-4-(CHNOCH3)cumyl trifluoroacetates are somewhat slower than that of 3,5-dimethylcumyl trifluoroacetate. This is attributed to steric inhibition of the cation-stabilizing resonance effect of the p-oximino group. In a 1-adamantyl system, where an α-oximino group has been placed directly adjacent to a developing cationic center, solvolysis rates relative to 1-adamantyl mesylate are slowed by a factor of 108. This is attributed a cation-destabilizing inductive effect where geometric constraints prevent stabilizing orbital overlap of the cationic center with the adjacent α-oximino group. This cation-destabilizing effect fades in the homoadamantyl and the bicyclo[3.3.1]nonyl systems, where rate-retarding effects are 1.6 × 104 and 1.5 × 102, respectively. The behavior of geometrically constrained α-oximino cations parallels that of analogously constrained allylic cations. Computational studies at the HF/6-31G* level indicate that twisting the α-oximino group out of planarity with a tertiary cationic center into a perpendicular arrangement decreases stabilization by 21 kcal/mol. These studies suggest that conjugative interactions, and not ground state destabilization, are the most important factors in controlling rates of formation of α-oximino cations from mesylates and trifluoroacetates.
Oxidation of organic compounds by ozone on a surface: 1. Ozonization of adamantane on silica gel
Avzyanova,Kabal'nova,Shereshovets
, p. 360 - 362 (1996)
Adamantanol was obtained by the ozonization of adamantane, at -78°C, adsorbed on silica gel. Ozone does not decompose on silica gel in the absence of a substrate. Ozonization of adamantane on silica gel is accompanied by chemiluminescence in the IR region. The chemiluminescence quenching is of first-order with the effective rate constant k′. In the range from 0.4 to 5 mmol, k′ depends linearly on the amount of adamantane adsorbed on the silica gel. The activation energy Ea = 9.97±1.89 kcal mol-1 and the pre-exponential factor A = (2.76±0.52)·106 were calculated from the temperature dependence of k′.
Dissociative electron transfer to dihaloalkanes. electrochemical reduction of 1,3-dihaloadamantanes, 1,4-dihalobicyclo[2.2.2]octanes, and 1,3-dihalobicyclo[1.1.1]pentanes
Adcock, William,Clark, Christopher I.,Houmam, Abdelaziz,Krstic, Alexander R.,Pinson, Jean,Savéant, Jean-Michel,Taylor, Dennis K.,Taylor, Julian F.
, p. 4653 - 4659 (1994)
The electrochemical reductive cleavage of the title compounds was investigated by means of cyclic voltammetry and electrolysis. The reaction is a two-electron process that yields competitively ring closure (or fragmentation) products and the monohalide resulting from the expulsion of the best leaving halide ion. Product selection occurs at the level of the carbanion resulting from the reduction of the one-electron reductive cleavage radical. In the formation of the latter, electron transfer and bond breaking are concerted; thus, the anion radical is not involved as an intermediate. The variations in the reduction potential observed in the three series of compounds can be rationalized, by application of the dissociative electron-transfer theory, as related variations of the bond dissociation energy of the first carbon-halogen bond to be cleaved. In the adamantane and bicyclopentane series, these are mainly the result of through-space-bonded interactions in the one-electron reductive cleavage radical and, to a lesser extent, in the starting dihalide itself, while through-bond interactions appear to prevail in the bicyclooctane series.
Hydrogen-atom and oxygen-atom transfer reactivities of iron(
Banerjee, Sridhar,Haukka, Matti,Hossain, Md. Kamal,Huelsmann, Ricardo Dagnoni,Martendal, Edmar,Munshi, Sandip,Nordlander, Ebbe,Paine, Tapan K.,Peralta, Rosely,Singh, Reena,Sinha, Arup,Valiati, Andrei Felipe,Wendt, Ola F.,Xavier, Fernando,Yiga, Solomon
supporting information, p. 870 - 884 (2022/02/01)
A series of iron(ii) complexes with the general formula [FeII(L2-Qn)(L)]n+ (n = 1, L = F?, Cl?; n = 2, L = NCMe, H2O) have been isolated and characterized. The X-ray crystallographic data reveals that
RUTHENIUM COMPLEX AND PRODUCTION METHOD THEREOF, CATALYST, AND PRODUCTION METHOD OF OXYGEN-CONTAINING COMPOUND
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Paragraph 0086-0097, (2021/01/29)
PROBLEM TO BE SOLVED: To provide a ruthenium complex that is particularly useful as a catalyst for oxidizing a substrate having a carbon-hydrogen bond. SOLUTION: The ruthenium complex represented by the general formula (i) or a cis conformer thereof is provided. In the general formula (i), R1 represents H, a phenyl group or a substituted phenyl group; R2 represents H, a phenyl group or an alkyl group; L1 represents halogen or water molecule; L2 represents triphenylphosphine, pyridine, imidazole or dimethylsulfoxide; X represents halogen; and n represents 1 or 2. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPO&INPIT
Cationic nickel(II) pyridinophane complexes: Synthesis, structures and catalytic activities for C-H oxidation
Nishimura, Tsubasa,Ando, Yuki,Shinokubo, Hiroshi,Miyake, Yoshihiro
supporting information, p. 1049 - 1052 (2021/05/19)
A series of nickel(II) pyridinophane complexes were synthesized and characterized by X-ray crystallographic analysis. Their IR spectra supported the existence of mononuclear nickel(II) complexes in solution. Furthermore, we conducted catalytic CH oxidation of cyclooctane with nickel(II) pyridinophanes as the catalysts. The activity of nickel(II) pyridinophanes was affected by steric hindrance around the nitrogen atoms.
