Verlaufen 1,3-Eliminierungen konzertiert oder nicht ?
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The labile cobalt (II) complex [Co(TUF)2(Pic)2] with 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (TUF) bidentate and 4-methylpyridine (Pic) monodentate ligands was studied by variable temp. (VT) 19F NMR from 184 to 312 K. In contrast to the solid state, ...
A convergent synthesis of all S-configurated diastereoisomer of RP-66453 (aS,S,S,S,S,S), a peptide secondary metabolite, has been developed. The synthesis is notable for its brevity, partly because functionalized amino acids can be used directly. By combin ...
The reactivity of the cluster family [Ru-3(CO)(12-x)(L)x] (in which L = PMe3, PMe2Ph, PPh3 and PCy3, x = 1 - 3) towards hydrogen is described. When x=2, three isomers of [Ru-3(H)(mu-H)(CO)(9)(L)(2)] are formed, which differ in the arrangement of their equa ...
An aq. soln. of peroxynitrous acid has been studied using first-principles mol. dynamics simulations based on d. functional theory. The relative Helmholtz energies of different conformers have been detd. via thermodn. integration with constraints. At contr ...
The reactivity of (E)- and (Z)-1-fluorobuta-1,3-diene ((E)- and (Z)-11), 2-fluorobutadiene (12). (E)and (Z)-1-(fluoromethylidene)-2-methylidenecyclohexane ((E)- and (Z)-13) toward SO2 has been explored and compared with that of (Z)- and (E)-1-(fluoromethyl ...
The introduction of a halogen atom at any arom. position of toluene considerably accelerates the base-promoted deprotonation of the Me group. P-Fluorotoluene is the only exception; proton abstraction from its benzylic site occurs approx. at one tenth of th ...
We have performed ab initio mol. dynamics simulations based on d. functional theory to characterize the structural, electronic, and dynamic properties of the three major isomeric forms of the title compd. In agreement with exptl. results, calcns. with two ...
The molecular complex [Re(equivalent toC(t)Bu)(=(CHBu)-Bu-t)((CH2Bu)-Bu-t)2] (1) reacts with a silica partially dehydroxylated at 700 degreesC to give syn-2, [(equivalent toSiO)Re(equivalent toC(t)Bu)(=(CHBu)-Bu-t)((CH2Bu)-Bu-t)], as a single isomer accord ...
The conformational analysis of a series of configurational isomers of 2-(hydroxymethyl)azepan-3,4,5,6-tetrols 1-4 has been carried out. H-1 NMR spectroscopic data, especially vicinal J couplings and nuclear Overhauser enhancements (NOE), assisted by molecu ...
Clusters of metal atoms at a fixed size can assume different structural arrangements, known as isomers, which may have nearly the same energy. Therefore at given experimental conditions distribution of these isomers can be present. While the size selection ...
