The Adamantane Rearrangement of Tricyclo[4.2.2.01,5]decane to Tricyclo[5.3.0.04,8]decane

Regioselective generation of the C(2)-carbocation a of tricyclo[4.2.2.0^1,5]decane ( 1 ) by treatment of both corresponding epimeric alcohols 5 and 6 with BF₃ and trapping the rearranged tricyclo[5.3.0.0^4,8]decan-7-yl carbocation b with Et₃SiH as hydride-ion donor (ionic hydrogenation) gives the corresponding hydrocarbon 3 as sole product in almost quantitative yield. The latter is a known intermediate in the Lewis-acid-catalyzed rearrangement of 1 to adamantane ( 4 ).     

Temperature dependence of electrical conductivity and thermoelectric power of Bi-Sb tapes prepared by liquid quenching

Electrical conductivity and thermoelectric power of liquid-quenched Bi-Sb tapes with Sb concentration in the range 8 to 18 at.% are reported between 77K and room temperature. Analysis of the data shows that the total electrical conductivity of these tapes is determined by a temperature-independent component due to band conduction, and a strongly temperature-dependent part due to carrier transport across or through the defect states. These defect states which appear to originate from structural imperfections and disorders due to rapid cooling, are formed close to the mobility edge within a small energy range.     

A simple analysis of the subband energies in quantum-confined non-parabolic semiconductors in the presence of a parallel magnetic field

Summary We study the subband energies in quantum wells and quantum wires in the presence of a parallel magnetic field in non-parabolic semiconductors, on the basis of a generalized dispersion relation considering all types of anisotropies of the energy-band parameters within the framework ofk·p formalism, by formulating the respective electron energy spectra. It is found, by takingn-Cd₃As₂ as an example, that the subband energies are greater for quantum wires and smaller for quantum wells, respectively. The magnetic field diminishes the above values and the corresponding well-known results for quantum-confined parabolic semiconductors have also been obtained from our generalized expressions under certain limiting conditions.     

Effect of magnetic quantization on the Einstein relation in Kane-type semiconductors

An attempt is made to formulate the Einstein relation for the diffusivity-mobility ratio of the carriers in degenerate semiconductors having Kane-type energy bands in the presence of a quantizing magnetic field, taking degenerate n-InAs as an example. It is found on the basis of the three-band Kane model, which is the most valid model for n-InAs, that the same ratio oscillates with changing magnetic field only under degenerate conditions and remains unaffected otherwise. The corresponding results for parabolic semiconductors are also obtained from the expressions derived.     

Stereospecific Synthesis of Endo-6-Aryl-2-Oxobicyclo [3.3.1]Nonanes

Two alternate synthetic routes to endo-6-aryl-2-oxobicyclo 3.3.1 nonan [3a-d] by sterespecific catalytic hydrogenetion of the easily accessible 6-arylbicyclo 3.3.1 nona-3,6-dien-2-ones [2a-d], and regioselective oomologation of endo-2-aryl-6-oxobicycle 3.2.1 octanes [4a-d] are described.     

Cyanuric chloride–dimethylformamide mediated cleavage of cyclopropylcarbinols-synthesis of phenolic antioxidant and construction of a new vinylcyclopropane skeleton

Differently substituted cyclopropylcarbinols underwent ring cleavage with easily accessible cyanuric chloride–N,N-dimethylformamide adduct to produce homoallylic chlorides or dienes depending on the nature and location of the substituents. A mechanistic explanation of the aforesaid observations has been provided. A promising antioxidant compound was prepared following this protocol and studied against Fenton’s reagent. This methodology was utilized to construct hitherto unreported vinylcyclopropane frameworks bearing homoallylic chloride and diene moieties.     

Mapping the Transformation [{RuII(CO)3Cl2}2]→[RuI2(CO)4]2+: Implications in Binuclear Water–Gas Shift Chemistry

The complete sequence of reactions in the base‐promoted reduction of [{Ru^II(CO)₃Cl₂}₂] to [Ru^I₂(CO)₄]²⁺ has been unraveled. Several μ‐OH, μ:κ²‐CO₂H‐bridged diruthenium(II) complexes have been synthesized; they are the direct results of the nucleophilic activation of metal‐coordinated carbonyls by hydroxides. The isolated compounds are [Ru₂(CO)₄(μ:κ²‐C,O‐CO₂H)₂(μ‐OH)(NP^F‐Am)₂][PF₆] ( 1 ; NP^F‐Am=2‐amino‐5,7‐trifluoromethyl‐1,8‐naphthyridine) and [Ru₂(CO)₄(μ:κ²‐C,O‐CO₂H)(μ‐OH)(NP‐Me₂)₂][BF₄]₂ ( 2 ), secured by the applications of naphthyridine derivatives. In the absence of any capping ligand, a tetranuclear complex [Ru₄(CO)₈(H₂O)₂(μ³‐OH)₂(μ:κ²‐C,O‐CO₂H)₄][CF₃SO₃]₂ ( 3 ) is isolated. The bridging hydroxido ligand in 1 is readily replaced by a π‐donor chlorido ligand, which results in [Ru₂(CO)₄(μ:κ²‐C,O‐CO₂H)₂(μ‐Cl)(NP‐PhOMe)₂][BF₄] ( 4 ). The production of [Ru₂(CO)₄]²⁺ has been attributed to the thermally induced decarboxylation of a bis(hydroxycarbonyl)–diruthenium(II) complex to a dihydrido–diruthenium(II) species, followed by dinuclear reductive elimination of molecular hydrogen with the concomitant formation of the Ru^I? Ru^I single bond. This work was originally instituted to find a reliable synthetic protocol for the [Ru₂(CO)₄(CH₃CN)₆]²⁺ precursor. It is herein prescribed that at least four equivalents of base, complete removal of chlorido ligands by Tl^I salts, and heating at reflux in acetonitrile for a period of four hours are the conditions for the optimal conversion. Premature quenching of the reaction resulted in the isolation of a trinuclear Ru^I₂Ru^II complex [{Ru(NP‐Am)₂(CO)}{Ru₂(NP‐Am)₂(CO)₂(μ‐CO)₂}(μ₃:κ³‐C,O,O′‐CO₂)][BF₄]₂ ( 6 ). These unprecedented diruthenium compounds are the dinuclear congeners of the water–gas shift (WGS) intermediates. The possibility of a dinuclear pathway eliminates the inherent contradiction of pH demands in the WGS catalytic cycle in an alkaline medium. A cooperative binuclear elimination could be a viable route for hydrogen production in WGS chemistry.     

On the two-dimensional thermoelectric power in quantum wells of non-parabolic materials under magnetic quantization

We present a simplified theoretical formulation of the thermoelectric power (TP) under magnetic quantization in quantum wells (QWs) of nonlinear optical materials on the basis of a newly formulated magneto-dispersion law. We consider the anisotropies in the effective electron masses and the spin–orbit constants within the framework of k.p formalism by incorporating the influence of the crystal field splitting. The corresponding results for III–V materials form a special case of our generalized analysis under certain limiting conditions. The TP in QWs of Bismuth, II–VI, IV–VI and stressed materials has been studied by formulating appropriate electron magneto-dispersion laws. We also address the fact that the TP exhibits composite oscillations with a varying quantizing magnetic field in QWs of n- Cd₃As₂, n- CdGeAs₂, n-InSb, p-CdS, stressed InSb, PbTe and Bismuth. This reflects the combined signatures of magnetic and spatial quantizations of the carriers in such structures. The TP also decreases with increasing electron statistics and under the condition of non-degeneracy, all the results as derived in this paper get transformed into the well-known classical equation of TP and thus confirming the compatibility test. We have also suggested an experimental method of determining the elastic constants in such systems with arbitrary carrier energy spectra from the known value of the TP.     

Matrix method for analysis of optical waveguides and quantum well structures

The one dimensional wave equation

Indomethacin: A NSAID sensitive to micro heterogeneity in alcohol–water mixtures

UV–vis absorption, steady state and time resolved fluorescence studies on the photo physical behavior of indomethacin, a traditional NSAID in binary water ethanol mixtures have been presented. Our results reveal that indomethacin can sense the micro heterogeneity in the binary mixtures forming ground state fluorescent complex with two predominant types of clusters viz. ethanol self-association clusters and hydrogen bonded water clusters.