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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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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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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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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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2,2'-Pyridyl- and 2,2'-thienylpyrroles containing substituents at the 1- and 3-positions of the pyrrole ring have been prepared from the reaction of heteroarylchlorocarbenes with 1-azabuta-1,3-dienes. Laser flash photolysis of heteroarylchlorocarbene in isooctane in the presence of 1-azabu...
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The reactions of the singlet methylene (la) and dimethylcarbene (1b), with their diazirine precursors, diazirine (2a), and dimethyldiazirine (2b), have been studied theoretically using ab initio and density functional theory. The reaction has no activation barriers for the parent system (la + 2a) an...