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The present thesis work provides new insight into the generation of allylmetal species and into their reactivity toward electrophiles. endo-Allylpotassiums are known to be more stable than their corresponding exo-isomers. The ring strain of methylenecycloa ...
Quinodimethanes are highly reactive toward dienophiles since Diels-Alder cycloaddn. results in an arom. product. D. functional-based 13C, 1H NMR, NICS, and MO-NICS calcns. indicate that the increase of arom. character of the developing benzenoid ring along ...
The first part of this work deals with oxidative addition reactions of the triangulo platinum cluster [Pt3(μ-CO)3(PCy3)3]. Reactions with the electrophilic molecules ICH2CN and X2 (X = I and Br) and with the weakly polar reagent Ph3SnH have been studied. A ...
Recently, we have introduced a scheme for optimizing atom-based nonlocal external potentials within the framework of d. functional theory (DFT) in order to systematically improve the description of mol. properties [Phys. Rev. Lett. 93, 153004 (2004); J. Ch ...
As observed by variable-temperature and -pressure C-13 NMR, intramolecular carbonyl scrambling in Ir2Rh2(CO)(12) and Ir-4(CO)(11)(mu-SO2) proceeds via a 'change of basal face' mechanism. In both cases the site exchange process has a positive activation vol ...
A visible-pump/UV-probe transient absorption is used to characterize the ultrafast dynamics of bacteriorhodopsin with 80-fs time resoln. We identify three spectral components in the 265- to 310-nm region, related to the all-trans retinal, tryptophan (Trp)- ...
An Ia mechanism was assigned for water exchange on the hexaaquaions Rh(OH2)63+ and Ir(OH2)63+ on the basis of negative ΔV⧧ experimental values (−4.2 and −5.7 cm3 mol-1, respectively). The use of ΔV⧧ as a mechanistic criterion was open to debate primarily b ...
Motion blending is widely accepted as a standard technique in computer animation, allowing the generation of new motions by interpolation and/or transition between motion capture sequences. To ensure smooth and seamless results, an important property has t ...
The regulation of the eukaryotic cell cycle depends on the action of several related Ser/Thr protein kinases called cyclin-dependent kinases (CDKs), which are transiently activated at specific stages of the cycle, and which are also very promising targets ...
(2,6-Dichlorophenyl)trimethyl- and triethylsilane exhibit untypical reactivity patterns toward strong bases: when treated at -100 °C with lithium 2,2,6,6-tetramethylpiperidide two, with sec- or tert-butyllithium even three organometallic intermediates are ...