Search results for "Transition State"
showing 10 items of 85 documents
N-doped carbon networks: alternative materials tracing new routes for activating molecular hydrogen.
2014
The fragmentation of molecular hydrogen on N-doped carbon networks was investigated by using molecular (polyaromatic macrocycles) as well as truncated and periodic (carbon nanotubes) models. The computational study was focused on the ergonicity analysis of the reaction and on the properties of the transition states involved when constellations of three or four pyridinic nitrogen atom defects are present in the carbon network. Calculations show that whenever N-defects are embedded in species characterized by large conjugated π-systems, either in polyaromatic macrocycles or carbon nanotubes, the corresponding H2 bond cleavage is largely exergonic. The fragmentation Gibbs free energy is affect…
Toward very potent, non-covalent organophosphonate inhibitors of cathepsin C and related enzymes by 2-amino-1-hydroxy-alkanephosphonates dipeptides
2013
Cathepsins play an important role in several human disorders and therefore the design and synthesis of their inhibitors attracts considerable interest in current medicinal chemistry approaches. Due to the presence of a strong sulphydryl nucleophile in the active center of the cysteine type cathepsins, most strategies to date have yielded covalent inhibitors. Here we present a series of non-covalent β-amino-α-hydroxyalkanephosphonate dipeptidic inhibitors of cathepsin C, ranking amongst the best low-molecular weight inhibitors of this enzyme. Their binding modes determined by molecular modelling indicate that the hydroxymethyl fragment of the molecule, not the phosphonate moiety, acts as a t…
Transition state theory thermal rate constants and RRKM-based branching ratios for the N((2)D) + CH(4) reaction based on multi-state and multi-refere…
2012
International audience; Multireference single and double configuration interaction (MRCI) calculations including Davidson (+Q) or Pople (+P) corrections have been conducted in this work for the reactants, products, and extrema of the doublet ground state potential energy surface involved in the N(2D) + CH4 reaction. Such highly correlated ab initio calculations are then compared with previous PMP4, CCSD(T), W1, and DFT/B3LYP studies. Large relative differences are observed in particular for the transition state in the entrance channel resolving the disagreement between previous ab initio calculations. We confirm the existence of a small but positive potential barrier (3.86 +/- 0.84 kJ mol-1…
Homochiral oxazolidin-2-ones and imidazolidin-2-ones by tandem nucleophilic addition–conjugate addition
2004
Abstract Treatment of both primary alcohols 1a , b and secondary amines 1c , d , tethered to a Michael acceptor with ( R )-phenylethyl isocyanate in the presence of DBU gave in good yield and high stereoselection diastereomeric mixtures of oxazolidin-2-ones 2a , b and 3a , b and imidazolidin-2-ones 2c , d and 3c , d , respectively. The cyclisation reaction was studied computationally by ab initio quantum mechanical methods. The observed stereoselectivity was explained on the basis of the different stability of both anions and transition states leading to 2a and 3a , respectively. The usefulness of the method was proven by conversion of 2a into the enantiomerically pure bioactive amino acid …
Kinetics and Mechanism of the Nucleophilic Substitution of Tellurium(II) Dialkanethiolates, Te(SR1)2 with Thiols, HSR2
2005
The equilibrium reaction between tellurium(II) dithiolates and thiols, Te(SR1)2 + 2 HSR2 ⇌ Te(SR2)2 + 2 HSR1 was studied by means of 1H- and 125Te NMR spectroscopy and ab initio quantum chemical methods. It was found that the reaction is catalyzed by Bronsted acids and bases, the catalytic activity corresponding to the strength of the respective acid or base. Investigation of the initial step of the reaction, Te(SR1)2 + HSR2 ⇌ Te(SR1)(SR2) + HSR1, showed it to proceed according to first order kinetics for Te(SR1)2, HSR2 and for the catalyst. Ab initio geometry optimizations and frequency calculations suggest [Te(SR1)(HSR1)(HSR2)]+ and [Te(SR1)2(SR2)]− to be stable intermediates and not tran…
Azo-hydrazo conversion via [1,5]-hydrogen shifts. A combined experimental and theoretical study
2012
Abstract Azoalkenes 6e , 6g , 6h , and 8c underwent an easy azo-hydrazo conversion via a [1,5]-hydrogen shift yielding α,β-unsaturated hydrazones. The isomerization products were characterized through spectroscopic and spectrometric techniques. In order to understand the nature of the mechanism of these [1,5]-hydrogen shifts, the transition state structures of the reactions were theoretically studied at the B3LYP/6-31G(d,p) level. Substitution effects in the propenylazo system on the kinetic and thermodynamic parameters were analyzed. An electron localization function (ELF) analysis of the electronic structure of the transition state structure associated with the azo-hydrazo conversion of t…
Photochemistry of 1,2,4-oxadiazoles. A DFT study on photoinduced competitive rearrangements of 3-amino- and 3-N-methylamino-5-perfluoroalkyl-1,2,4-ox…
2006
The photoinduced competitive rearrangements of 5-perfluoroalkyl-3-amino(N-alkylamino)-1,2,4-oxadia- zoles have been investigated by DFT calculations and UV-vis spectroscopy. The observed product selectivity depends on the number of hydrogen atoms present in the amino moiety and involves two or three possible routes: (i) ring contraction-ring expansion (RCRE), (ii) internal-cyclization isomerization (ICI), or (iii) C(3)-N(2) migration-nucleophilic attack-cyclization (MNAC). UV absorption and fluorescence spectra of the reactants, and vertical excitation energy values, calculated by time dependent DFT, support the involvement of a neutral singlet excited state in the photoexcitation process. …
Transition state ensemble optimization for reactions of arbitrary complexity.
2015
In the present work, we use Variational Transition State Theory (VTST) to develop a practical method for transition state ensemble optimization by looking for an optimal hyperplanar dividing surface in a space of meaningful trial collective variables. These might be interatomic distances, angles, electrostatic potentials, etc. Restrained molecular dynamics simulations are used to obtain on-the-fly estimates of ensemble averages that guide the variations of the hyperplane maximizing the transmission coefficient. A central result of our work is an expression that quantitatively estimates the importance of the coordinates used for the localization of the transition state ensemble. Starting fro…
Location of transition states and stable intermediates by MINIMAX/MINIMI optimization of synchronous transit pathways
1983
The MINIMAX/MINIMI concept for the location of transition states and/or stable intermediates of chemical reactions is introduced, based on the synchronous transit method. According to this strategy, minimization of quadratic synchronous transit path maxima or minima is achieved by constrained exhaustive optimization of internal coordinates. The method and its efficiency are demonstrated for two-dimensional model surfaces as well as for thermally allowed electrocyclic interconversions of cyclopropyl-/allyl-cation and cyclobutene-/butadiene (gauche) within the framework of MNDO-SCF calculations. Thus, in both cases a direct comparison with the exact solution determined by minimization of the …
Fission fragment angular distributions in the capture reactions 50Ti, 56Fe + 208Pb
2008
The analysis of %-ray mult ip l ic i t ies measured I in coincidence with capture fission events in reactions of 26Mg through 54Cr, 58Fe, and 64Ni with 208pb in terms of Ko and~eff revealed1 that the resulting values of ~ /~e f f were rather independent of for a given system and, in a compound nucleus picture, were more in agreement with the 'shape of the non-rotating saddle than with the actually expected rotating saddle I f non-compound systenmhave to be considered these values of ~/J~ff__ shapes. suggested at least that the captured systems near the turning point from the inward radial motion to symmetric fragmentation had reached a remarkable compactness.