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Abstract: We report here the results on single crystal X-ray crystallographic analysis of the Gd@C82 carbene adduct (Gd@C82(Ad), Ad = adamantylidene). The Gd atom in Gd@C82(Ad) is located at an off-centered position near a hexagonal ring in the C2v-C82 cage, as found for M@C82 (M = Sc and La) and La...
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The article presents a research which discusses the preparation and characterization of the nanorods of the endohedral metallofullerene derivative lanthanum (La)@carbon(C)82(Ad). The nanorods of La@C82(Ad) were prepared by a liquid-liquid interfacial precipitation method. The s...
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Abstract: The photochemical reaction of M2@C80 (M = La and Ce) with 2-adamantane-2,3'-[3H]-diazirine (1) affords the corresponding adducts by carbene addition. The adducts were characterized by spectroscopic and single-crystal X-ray structure analyses. Crystallographic data for the adduct La2@C80(Ad...
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By employing C-60 as a chemical probe, the photolysis of benzylchlorodiazirine has been proposed to form carbene and the rearranged products via the excited state. (c) 2006 Elsevier Ltd. All rights reserved.
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Phenylchlorocarbene, generated by photolysis or thermolysis of the phenylchlorodiazirine, reacts with 2,2'-bipyridyl to give, in alkane solvents, the 6-phenyldipyrido[1,2-c:2',1'-e]i-midazolium chloride. We investigated the mechanism of the reaction by flash photolysis. Like the mechanism of formati...
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C-60 acts as a mechanistic probe for the formation of carbene and for the rearranged product via the excited state in the photolysis of 3-t-butyl-3-chlorodiazirine. (C) 2004 Published by Elsevier Ltd.
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The analysis of the time-resolved UV-vis absorption spectra of the 2-vinylpyridinium ylide of phenylchlorocarbene, measured by laser-flash photolysis, indicates the existence of two rotamers of this species. The absorption spectrum, rise time, and decay time of each rotamer were determined by a glob...
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The photolysis of m-phenylene-bis(chlorodiazirine) in the presence of 2-vinylpyridine (VP) yields the m-phenylene-bis(indolizine) by a mechanism involving two consecutive photoreactions. Photolysis of a first diazirine ring generates a carbene which reacts with 2-VP to give, via a sequence of fast t...
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Reaction of adamantylidene and phenylcarbene with ethylthiol, ethylene dithiol, allylethylsulfide, allylphenylsulfide, and trimethylenesulfide involves the formation of a sulfur ylide intermediate, followed by H-migration, 2,3-sigmatropic shift, or ring opening to give sulfides. The sulfur ylide for...
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The thermal decomposition of phenylehlorodiazirine (1), phenyl-n-butyldiazirine (2), and 2-adamantane-2,3'-[3H] diazirine (3) has been studied in solution in the presence Of C-60. The C-60 probe technique indicates that in the decomposition diazirine 1 yielded exclusively phenylchlorocarbene, diazir...
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C-60 acts as a mechanistic probe for the formation of carbene, diazo compound, and for the rearranged product via the excited state in the photolysis of 3-chloro-3-isopropyldiazirine and 3-chloro-3-chloromethyldiazirine. The carbene adds to C-60 to form methanofullerene, whereas the diazo compound a...
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Reaction of arylchlorodiazirines with trimethylenesulfide gives a mixture of aryldi(3-chloropropyl)thioacetal and aryl(2-propenyl)(3-chloropropyl)thioacetal in a good yield. The reaction goes through a formation of a sulfur ylide as an intermediate. Rate constants have been determined using laser fl...
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Substituted pyrazoles and pyrrolo[1,2-c]pyrimidines were prepared from the reaction of arylchlorocarbenes with 1,2-diazabuta-1,3-dienes and 4-vinylpyrimidines, respectively.
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The formation of a metastable carbene-diazirine ylide (CDY), characterized by an UV absorption spectrum in the range of 270-290 nm and yielding azine by rearrangement, is shown to be a general process in the photolysis of diazirines. However, the yield of formation and the lifetime of CDY greatly de...
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Laser Flash Photolysis of arylchlorodiazirines in isooctane/CH2Cl2 in the presence of substituted vinylpyridines yields substituted vinylpyridinium ylide (lambda = 540 nm). As the ylide decays a concomitant growth causes an absorption at 330 nm, attributed to the formation of substituted indolizine....
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1,2,3-Trisubstituted pyrroles have been synthesized in good yield from the reaction of chlorocarbenes with 1-azabuta-1,3-dienes.