Search results for "transition"

Theoretical and Spectroscopic Studies On Imino-carbon Palladated Pyridine-2-carbaldimines

1987

Abstract Ab initio LCAO-MO-SCF calculations on the model compounds C 5 H 4 N-2-C(R 1 )=NH [R 1 = H ( 2c ) and R 1 = trans -PdCl(PH 3 ) 2 ( 4c )] indicate that the E - trans conformation is favored over the E - cis one by 16.9 kJ mol −1 for 2c and by 25.0 kJ mol −1 for 4c . One of the factors which stabilizes the E-trans arrangement for 4c is a weak bonding interaction between the palladium center and the pyridine nitrogen. On going from 2c to 4c a slight charge enrichment on the pyridine carbons and a more pronounced one on the nitrogen atoms is computed, whereas the charge density of the imino carbon atom is decreased. In 4c no π contribution to the PdC bond is observed. Protonation of th…

Spin transition in heptanuclear star-shaped iron(III)–antimony(V) NCS- and CN-bridged compounds

2009

Abstract The precursor [FeIII(L)Cl] (LH2 = N,N′-bis(2′-hydroxy-benzyliden)-1,6-diamino-3-azahexane) has been prepared and Mossbauer spectroscopy assigned a high-spin (S = 5/2) state at room temperature. The precursor is combined with the bridging units [SbV(X)6]− (X = CN−, NCS−) to yield star-shaped heptanuclear clusters [(LFeIII–X)6SbV]Cl5. The star-shaped compounds are in general high-spin systems at room temperature. On cooling to 20 K some of the iron(III) centers switch to the low-spin state as indicated by Mossbauer spectroscopy, i.e. multiple electronic transitions. While the cyano-bridged complex performs a multiple spin transition the thiocyanate-compound shows no significant popul…

Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl clusters – diastereomeric control o…

2020

Twenty clusters of the general formula [(μ-H)2Ru3(μ3-S)(CO)7(μ-P–P*)] (P–P* = chiral diphosphine of the ferrocene-based Walphos or Josiphos families) have been synthesised and characterised. The clusters have been tested as catalysts for asymmetric hydrogenation of tiglic acid [trans-2-methyl-2-butenoic acid]. The observed enantioselectivities and conversion rates strongly support catalysis by intact Ru3 clusters. A catalytic mechanism involving an active Ru3 catalyst generated by CO loss from [(μ-H)2Ru3(μ3-S)(CO)7(μ-P–P*)] has been investigated by DFT calculations. peerReviewed

Oxygen Radical Scavengers

2010

The myocardium can tolerate only relatively short periods of total myocardial ischemia without myocardial cell death. Following short ischemic periods, ischemic damage is reversible by reperfusion. However, with increasing duration and severity of ischemia, the damage inflicted to cardiomyocytes following reperfusion becomes irreversible. The combined pathologic events in the myocardium that follow a critical period of ischemia and leading to either reversible or irreversible damage to both cardiomyocytes and cardiac microvasculature is known as ischemia-reperfusion injury (Goldhaber and Weiss 1992).

Absorption spectrum of the f(A1g) ← X(Eg), a(F2g) electronic transition of OsF6

1997

Abstract The absorption spectrum of the visible band of OsF 6 has been recorded using a commercial spectrophotometer. The first vibronic assignments for this band have been realized using the analogy with the d ← X transition of IrF 6 . Some vibronic parameter values are derived.

Designing a Transition State Analogue for the Disfavored Intramolecular Michael Addition of 2-(2-Hydroxyethyl)acrylate Esters

1999

The rate-determining steps for the intramolecular 1,2 and 1,4 addition reactions in basic medium of methyl 2-(2-hydroxyethyl)acrylate to give the corresponding γ-lactone and tetrahydrofuran, respec...

Properties of Multi Phase Interfaces on the Tungsten Trioxide Particles in the Thin Films

2000

A wide spectrum of physical and chemical properties of thin films of tungsten trioxide compounds depend on composition, constitution and structure of the film, interaction with environment, and the type of external influences/excitations. The reason is the non-stoichiometric nature of transition metal oxides and properties of d-electrons. The short range order of non-stoichiometric compounds or phases of WO3 has a strong perovskite arrangement of tungsten and oxygen ions [1, 2]. The smallest crystalline clusters of perovskite short range order consist 6÷9 of [WO6]-octahedrons. One of the structural peculiarities-features of tungsten trioxide, related to non-stoichiometry, is a variety of [W…

1991

Red- and Blue-Shifts in Oligo(1,4-phenyleneethynylene)s Having Terminal Donor−Acceptor Substitutions

2004

Four series of oligo(1,4-phenyleneethynylene)s (OPEs), 1−4 (a−d), each having a terminal dialkylamino group as their electron donor, were prepared by applying Sonogashira−Hagihara reactions and a protecting group strategy. To study the influence that the push−pull effect has on the long-wavelength absorption, three of the four series of OPEs contain terminal acceptor groups (CN, CHO, NO2). Extending the conjugation (increasing the number of repeat units, n) lowers the energy E(n) of the electron transition in the purely donor-substituted series 1a−4a (bathochromic shift). This effect is superimposed in the push−pull series 1−4 (b−d) by the effect of the intramolecular charge transfer (ICT),…

A coupled cluster calculation of the spectrum of urea

2001

Several coupled cluster methods have been used to compute the vertical excitation energies and oscillator strengths of the lowest singlet states of urea. Except for one excitation, the results are in good agreement with experiment, but previously non-detected transitions have been found.