In: The Journal of Physical Chemistry A, 2010, vol. 114, no. 25, p. 6787–6794
The primary products, i.e., the radical cations and radicals obtained on oxidation of the glucobrassicin metabolites (and dietary supplements), indole-3-carbinol (I3C) and diindolylmethane (DIM), and those from parent indole (I) are characterized in an ionic liquid and in Ar matrices. The radical cations of I and I3C are stable toward (photo)deprotonation under these conditions, but the resulting...
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In: Chemistry, a European Journal, 2010, vol. 16, no. 24, p. 7121–7124
In contrast to the structurally and configurationally stable alkyl- or aryl-substituted cyclopropyl radical cations, cyclopropyl silyl ethers undergo spontaneous ring opening upon oxidation whereby the endocyclic C-C(O-TMS) bond is cleaved with remarkable selectivity. DFT calculations on 1-trimethylsilyloxybicyclo[4.1.0]heptane show that this selectivity arises from the topology of the potential...
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In: Nature Chemistry, 2010, vol. 2, no. 3, p. 165-166
Electromerism is an unfamiliar concept to many chemists and refers to molecules that are not conventional isomers but instead differ in how the electrons are distributed across their structure. A novel example of such electromers has now been demonstrated.
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In: Angewandte Chemie International Edition, 2010, vol. 49, no. 2, p. 399-402
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In: The Journal of Organic Chemistry, 2009, vol. 74, no. 11, p. 4017–4023
The purpose of this paper is to convince practitioners of ¹H NMR spectroscopy to consider simple quantum chemical calculations as a viable option to aid them in the assignment of their spectra. To this end, it is demonstrated, on a test set of 80 conformationally stable molecules of various kinds carrying different functional groups, that, in contrast to what is claimed in the literature, large...
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In: Inorganic Chemistry, 2009, vol. 48, no. 9, p. 4075–4082
To elucidate the multifaceted but poorly understood chemistry of the pivotal polysulfur−nitrogen heterocycle, tetrasulfur tetranitride (S₄N₄, 1), its photochemistry was studied in Ar matrices. Thereby two primary intermediates and a secondary one (2−4) were detected, and their UV−vis and IR spectra were identified through specific interconversions of...
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In: Chemistry - A European Journal, 2009, vol. 15, no. 7, p. 1604 - 1617
Low-energy electronic transitions have been detected spectroscopically in the FeII-FeIII mixed-valent biferrocenyl radical cation, but are absent in the spectra of the neutral analogue. They have been assigned by time-dependent DFT calculations (squares in figure). Analogous investigations were performed for the bisfulvalenide FeII-FeIII radical cation....
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In: Journal of the American Chemical Society, 2007, vol. 129, no. 26, p. 8380-8388
p-Biphenylyl, o-biphenylyl, and 1-naphthyl azides were deposited in argon at low temperature in the presence and absence of HCl. In the absence of HCl, the known electronic and vibrational spectra of the corresponding triplet nitrenes, azirines, and didehydroazepines were observed, whereas in the presence of HCl, photolysis of these azides produces new electronic spectra assigned to...
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In: Chimia, 2007, vol. 61, no. 10, p. 645-649
This paper illustrates the research on the photochemistry of reactive intermediates that was (and still is) carried out in the author's research group on three typical examples: the photochemistry of arylcarbenes, arylnitrenes, and organic radical cations.
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In: The Journal of Physical Chemistry A, 2007, vol. 111, no. 5, p. 817 -824
Photolysis of 1,3,2,4-benzodithiadiazine (1) at ambient temperature yields stable 1,2,3-benzodithiazolyl radicals. In order to reveal the mechanism of this unusual transformation, the photochemistry of 1 was studied in argon matrices using IR and UV-vis spectroscopy. A series of intermediates, including four- and five-membered heterocyclic and o-quinoid acyclic species, were characterized...
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