Bonding and Reactivity in RB-As R Systems(R=H,F,OH,CH_3,CMe_3,CF_3,SiF_3,BO): Substituent Effects

Density functional theory-based calculations have been carried out to study the bonding and reactivity in RB-As R(R=H,F,OH,CH3,CMe_3,CF_3,SiF_3,BO)systems.Our calculations demonstrated that all the studied systems adopted bent geometry(DR-B-As≈180°andDB-As-R≈90°or less).The reason for this bending was explained with the help of a valence-orbital model.The potential energy surfaces for three possible isomers of RB-As R systems were also generated,indicating that the RB-As R isomer was more stable than R_2B-As R when R=SiF_3,CMe_3,and H.The B-As bond character was analyzed using natural bond orbital(NBO)and Wiberg bond index(WBI)calculations.The WBI values for B-As bonds in F3Si B-As SiF_3 and HB-As H were 2.254 and 2.209,respectively,indicating that this bond has some triple-bond character in these systems.While the B centers prefer nucleophilic attack,the As centers prefer electrophilic attack.     

Metal-free synthesis of secondary amines by the reaction of tosyl triazene and aryl boronic acid

A metal free noncatalytic amination process has been developed for the synthesis of N-substituted aniline using a new amine source. The amine source p-toluene sulfonyl triazene (PhN?NNHTs) has been prepared by treating aryldiazonium salt with p-tosylamide. Various unsymmetrical amines could be synthesized by treating this reagent and boronic acid in toluene at 110?°C in the presence of DBU and 4?Å molecular sieve. A large variety of N-substituted aniline could be synthesized with moderate yield.     

Regioselective addition of 1,3-dicarbonyl dianion to N-sulfonyl aldimines: an expedient route to N-sulfonyl piperidines and N-sulfonyl azetidines

A simple route for the synthesis of δ-amino-β-keto esters and δ-amino-β-diketones is reported. This involves regioselective addition of 1,3-dianions derived from ethyl acetoacetate and acetyl acetone to N-sulfonyl aldimines. The δ-amino-β-keto ester derivatives were further converted into the corresponding N-sulfonyl piperidines and N-sulfonyl azetidines.     

Lewis acid mediated nucleophilic ring opening followed by cycloaddition of 2-aryl-N-tosylaziridines with carbonyl compounds: further support towards an SN2-type mechanism

A highly regioselective S_N2-type ring opening of 2-aryl-N-tosylaziridines with carbonyl compounds in the presence of a Lewis acid to afford various 1,3-oxazolidines and 1,2-amino alcohols in excellent yields and moderate to high enantioselectivity is described. The formation of non-racemic products provides convincing evidence for the S_N2-type ring opening mechanism.     

Linear and nonlinear response of 2-D single carrier dots: Role of impurity perturbations

Linear and non-linear optical response of impurity perturbed 2-D single carrier quantum dots have been computed by finite field linear variational method. We have considered Gaussian and exponential impurity centres of both repulsive and attractive types. The signatures of various parameters like the intensity of the magnetic field, confinement strength, nature and the strength of the impurity perturbation, on the responses are analysed. It appears that with proper choice of system parameters, any kind of response can be realized.     

Supramolecular interactions of [60]- and [70]fullerenes with calix[n]arenes

[60]- and [70]fullerenes have been shown to form 1:1 supramolecular complexes with (i) 24,26-dimethoxy-25,27-dihydroxy-5,11,17,23-tetra(4-tert-butyl)calix[4]arene (1) and (ii) 37,39,41-trimethoxy-38,40,42-trihydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (2) in CCl(4) medium by absorption spectroscopy. Charge transfer absorption bands of the complexes have been located in each of the cases (except [70]fullerene-2 complex) studied from which the vertical ionisation potential of 1 has been obtained. Formation constants of the complexes have been determined at four different temperatures from which the enthalpies and entropies of formation of the complexes have been obtained. Moreover, the formation constant of [70]fullerene-2 complex is higher than that of the [60]fullerene-1 and [60]fullerene-2 complexes at all the four temperatures studied. This has been accounted in terms of greater cavity size of 2 which is a calix[6]arene compared to 1 which is a calix[4]arene and also by the fact that a high degree of preorganisation takes place in case of 2 through intramolecular H-bonding at its lower rim.     

Energies of charge transfer and supramolecular interactions of some mono O-substituted calix[6]arenes with [60]fullerene by absorption spectrometric method

Equilibria for the formation of supramolecular complexes of [60]fullerene with a series of mono O-substituted calix[6]arenes, namely: (i) 37-methoxy-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (1), (ii) 37-allyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (2), (iii) 37-phenacyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (3), (iv) 37-ethylester-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (4) and (v) 37-benzyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (5) have been studied in CCl4 medium by absorption spectroscopic technique. The stoichiometry has been found to be 1:1 ([60]fullerene:calix[6]arene) in each case. An absorption band due to charge transfer (CT) transition is observed in each case in the visible region. The vertical ionisation potentials (I(D)(v)) of all the calix[6]arenes under study have been estimated utilising CT transition energy. The experimental I(D)(v) values also yield a good estimate of the electron affinity of [60]fullerene. The degrees of CT in the ground state of the complexes have been found to be very low (about 0.15%). Resonance energy of the complexes have been estimated. Thermodynamic parameters for the supramolecular complex formation of [60]fullerene with mono O-substituted calix[6]arene receptors are reported. It is observed that among the calix[6]arenes under the present study, only 1 and 4 form inclusion complexes with [60]fullerene. This has also been substantiated by theoretical calculation using PM3 method. Thus presence of one substituent group (of different types) on the lower rim of the calix[6]arene molecule has been shown to govern the host-guest complexation process.