70 research outputs found
Prototropic and metallotropic migration of isolobal fragments on indol rings. Theoretical study and NBO analysis
Molecular structures, energies, NBO analysis and sigmatropic behaviour of 1-Indenyl(dihydro)borane (1) and 1-Indenyl-threecarbonylcobalt(I) (2) were investigated using DFT and ab initio molecular orbital methods. In these compounds BH2 and Co(CO)3 fragments areisolobal. The Results of calculations using B3LYP, HF and MP2methods [Basis set 6-311+G**] showed that -BH2 and -Co(CO)3 had similar behaviour in sigmatropic shifts. Prototropic shifts in compounds 1 and 2 have similar mechanisms too. Results showed that metallotrotropic shift is faster than Prototrpic shift in compounds 1 and 2. The activation energies (Ea) of Prototropic shift in compounds 1 and 2 are 18.83 and 17.38 kcal.mol-1. These energies are higher than -BH2 shifts in compound 1 (10.11 kcal.mol-1) or migration of -Co(CO)3 fragment in compound 2 (12.39 kcal.mol-1). Lower amount of activation energy in borotropic shift and cobalt`s fragment shift show that rotation of boron and cobalt on the indol ring can happen in the ambient temperature. Calculation results revealed that migration of proton and Co(CO)3 was carried out via suprafacial[1,2]-sigmatropic mechanism while -BH2 shift took place via antrafacial [1,3]-rearangment.Ă‚
Complexes of thallium(I) and cadmium(II) with dipeptides of L-phenylalanylglycine and Glycyl-L-phenylalanine
The stability constants of the complexes of thallium(I) and cadmium(II) ions with dipeptides of glycyl-L-phenylalanine and L-phenylalanylglycine were determined in aqueous solution at 25 ÂşC and 0.1 mol dm-3 ionic medium using a combination of potentiometric and spectrophotometric techniques. Sodium perchlorate was used to maintain the ionic strength. The composition of the formed complexes was determined and it was shown that thallium(I) and cadmium(II) forms two mononuclear 1:1 species with the ligands, of the type [Tl(HL)]+, TlL, [Cd(HL)]2+ and [CdL]+ in the pH range of study (1.5-10.5), where L represents a fully dissociated ligand. The logarithms of the cumulative stability constants, betaxyz, of the complexes, [(Metal ion)x(H+)y(ligand) z], are log beta111 and log beta101: 12.15, 3.39 (for Tl+ with L-phenylalanylglycine), 11.36, 2.13 (for Tl+ with glycyl-L-phenylalanine), 12.06, 2.82 (for Cd2+ with L-phenylalanylglycine), 10.70 and 1.70 (for Cd2+ with glycyl-L-phenylalanine), respectively
Complete basis set, hybrid-DFT study and NBO interpretations of conformational behaviors of trans-2,3- and trans-2,5-dihalo-1,4-dithianes
Natural Bond Orbital Theory of Pseudo-Jahn–Teller Effects
We describe a unified
picture of symmetry-breaking electronic interactions
that are usually described as “pseudo-Jahn–Teller (PJT)
effects” and attributed to vibronic coupling but can also be
associated with hyperconjugative donor–acceptor interactions
in the framework of natural bond orbital (NBO) and natural resonance
theory (NRT) analysis. We show how NBO/NRT descriptors offer a simplified
alternative to the vibronic coupling picture of PJT effects that yields
both improved cause–effect specificity and chemically enriched
understanding of symmetry-breaking phenomena but with no necessary
input from ground-state vibrational or excited-state electronic properties.
Comparative NBO/NRT vs vibronic coupling analyses of PJT effects are
illustrated for two well-known cases: trans-bending in Si<sub>2</sub>H<sub>4</sub> and higher Group-14 homologues of ethylene and chain-kinking
in cyclopentadienylideneketene (C<sub>5</sub>H<sub>4</sub>CCO) and
related cumulene ketones. The conceptual and practical advantages
of the NBO-based hyperconjugative approach may be expected to extend
to numerous PJT-type symmetry-breaking phenomena throughout the chemical
sciences
Investigation of kinetic and mechanism of triphenylphosphine addition topara-naphthoquinone
On the Covalent Character of Rare Gas Bonding Interactions: A New Kind of Weak Interaction
At the averaged quadratic coupled-cluster (AQCC) level,
a number
of selected rare gas (Rg) containing systems have been studied using
the quantum theory of atoms in molecules (QTAIM), natural bond orbital
(NBO), and several other analysis methods. According to the criteria
for a covalent bond, most of the Rg–M (Rg = He, Ne, Ar, Kr,
Xe; M = Be, Cu, Ag, Au, Pt) bonds in this study are assigned to weak
interactions instead of van der Walls or covalent ones. Our results
indicate that the rare gas bond is a new kind of weak interaction,
like the hydrogen bond for example
Configurational Properties of N,N′-Dimethyl-1,3-Diazacyclohexane and Its Analogues Containing P and As Atoms: A Hybrid-DFT Study and NBO Interpretation
Exploring the Origin of the Generalized Anomeric Effects in the Acyclic Nonplanar Systems
Contrary to the published conclusions
in the literature concerning the origin of the generalized <i>anomeric</i> relationships in open-chain nonplanar systems,
its origin has remained an open question. In order to explore the
origin of the generalized <i>anomeric</i> relationships
in open-chain nonplanar systems, we assessed the roles and contributions
of the effective factors on the conformational properties of methyl
propargyl ether (<b>1</b>), methyl propargyl sulfide (<b>2</b>), and methyl propargyl selenide (<b>3</b>) by means
of the G3MP2, CCSDÂ(T), MP2, LC-ωPBE, and B3LYP methods and natural
bond orbital (NBO) interpretations. We examined the contributions
of the hyperconjugative interactions on the conformational preferences
of compounds <b>1</b>–<b>3</b> by the deletions
of the orbitals overlapping from the Fock matrices of the <i>gauche</i>- and <i>anti</i>-conformations. The trend
observed for energy changes in the Fock matrices justify the variations
of the <i>gauche</i>-conformations preferences going from
compound <b>1</b> to compound <b>3</b>, revealing that
the hyperconjugative interactions are solely responsible for the generalized <i>anomeric</i> relationships in compounds <b>1</b>–<b>3</b>. Accordingly, the conclusions published in the literature
concerning the origin of the generalized <i>anomeric</i> effect in the acyclic nonplanar compounds should be revised by these
findings. The Pauli exchange type repulsions (PETR) are in favors
of the <i>gauche</i>-conformations and the variations of
the PETR differences between the <i>gauche</i>- and <i>anti</i>-conformations of compounds <b>1</b>–<b>3</b> correlate well with their <i>gauche</i>-conformations
preferences, revealing that the generalized <i>anomeric</i> relationships in compounds <b>1</b>–<b>3</b> have
also the Pauli exchange-type repulsions origin. The resemblance between
the preorthogonal natural bond orbitals (that are involved in the
hyperconjugative interactions) and their corresponding molecular orbitals
have been investigated
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