Both flash vacuum thermolysis (FVT) and matrix photolysis generate 2-diazomethylpyrazine (22) from 1,2,3-triazolo[1,5-a]pyrazine (24). FVT of 4-azidopyridine (18) as well as of 24 or 2-(5-tetrazolyl)pyrazine (23) affords the products expected from the nitrene, i.e., 4,4'-azopyridine and 2- and 3-cyanopyrroles. Matrix photolyses of both 18 and 24 result in ring expansion of 4-pyridylnitrene/2-py...

From the A-dihydrobilindione 3. the pyridinium derivatives 6a,b and analogues therwf have been obtained by a formal nucleophilic substitution. The reaction is rationalized as a photochemically assisted oxidation of 3 with a subsequent regioselective addition of pyridine at C-5. By thermolysis. 6a.b yields back the parent bilin 3, together with an oxidation product. The significance of the react...

This paper presents an overview of the principles of hydrogen energy production, storage, and util ization. Hydrogen production wil l cover a whole array of methods including electrolysis, thermolysis, photolysis, thermochemical cycles, and production from biomass. H ydrogen storage will cover al l modes of gaseous, liquid, slush, and metal hydride storage. Hydrogen uti l ization will focus on ...

Open-shell phosphanyl complexes (OC)5W{(Me3Si)2HCP(X)} (X = F, H), obtained by one-electron oxidation of lithium phosphanido complexes, were trapped by TEMPO to yield novel thermally labile P-nitroxyl phosphane complexes. First experimental evidence for an open-shell P-F phosphanoxyl complex (OC)5W{(Me3Si)2HCP(O)F}, formed upon thermolysis of corresponding P-nitroxyl derivative, is reported; re...

Iminopropadienones, RN=C=C=C=O, can be generated from four different types of precursors in flash vacuum thermolysis reactions: 1,3-dioxane-4,6-diones 1, isoxazolopyrimidinones 2, pyridopyrimidinium olates 3, and pyridopyrimidinones 4. 2,6-Difluorophenyl-, 2,6-diethylphenyl-, o-tert-butylphenyl-, and mesityliminopropadienone have been directly observed by Ar matrix IR spectroscopy in one or mor...

Mild thermolysis of tert-butyl alkynyl ethers furnishes aldoketenes, which undergo facile [2 + 2] cycloaddition reactions with pendant di- and trisubstituted alkenes. A wide variety of cis-fused cyclobutanones are produced in moderate to high diastereoselectivity and good to excellent yields by this method, and free hydroxyl groups are tolerated in the ene-ynol ether starting materials. Enol-yn...

The PdTe NPs (hexagonal) and nanorods (first example) have been synthesized for the first time from single source precursors (SSPs), [Pd(L1)Cl2] (1) and [Pd(L2)Cl]BF4 (2) [L1, 4-bromo-1-[2-(4-methoxyphenyltellanyl)ethyl]-1H-pyrazole; L2, bis-[2-(4-bromopyrazol-1-yl)ethyl]telluride], by their thermolysis in an OA–ODE mixture (1:1) and TOP respectively. The composition of the PdTe phase does not ...

While thermolysis of the macrobicyclic triene lactone 12 did not produce the expected bicyclic transannular Diels-Alder (BTADA) product 13, heating the corresponding ether 18 to 110 °C for 4 h afforded a quantitative yield of the desired cycloadduct 19, which could be easily reduced to the perhydrophenanthrene, an ABC ring analogue of fusidic acid 1. Theoretical calculations with hybrid density...