The effects of halogens; fluorine, chlorine and bromine, on the stability and multiplicity of phenylcarbenes / silylenes/ germylenes structures are compared and contrasted at B3LYP/6-311++G**//B3LYP/6-31+G* level. The singlet-triplet energy gaps, ΔES-T , values for all the above speciesincrease through fluorinated up, ΔES-Ts and ΔEHOMO–LUMOs support the stability of the singlet statesinspite of...

A three component reductive coupling reaction of a (hetero)aromatic amine, a (hetero)aromatic aldehyde and an electron deficient olefin catalysed by eosin Y under green LED light irradiation, for the direct generation of γ-amino acid derivatives, is described. This new umpolung synthesis of amines, which exploits the high nucleophilicity of a putative α-amino radical intermediate, generated via...

This study permits to explore the interactions involved in Lewis acid (AlH3) and bases: CO; H2O; NH3; PH3; PC13; H2S; CN–; OH–; O2–2; F–; N(CH3)3; N2; N2H4; N2H2; C5H5N; C6H5-NH2. By means of DFT theory calculations with B3LYP functional using 6-31G(d,p) basis set order check effects both donor acceptor establishment different adducts we focused mainly on calculation energetic gap ∆EHOMO-LUMO, ...

The solvolyses of 4-fluorophenyl chlorothionoformate (1) are studied in fifteen binary aqueous organic mixtures of widely varying nucleophilicity and ionizing power values. The specific rates of solvolyses of 1 are plotted against the specific rates of solvolysis observed for phenyl chloroformate (2) and deviations from the line-of-best-fit are observed in some of the highly ionizing aqueous fl...

The "parent" tertiary alkyl chloroformate, tert-butyl chloroformate, is unstable, but the tert-butyl chlorothioformate (1) is of increased stability and a kinetic investigation of the solvolyses is presented. Analyses in terms of the simple and extended Grunwald-Winstein equations are carried out. The original one-term equation satisfactorily correlates the data with a sensitivity towards chang...

Abstract — Allylsilanes undergo regiospecific reactions with a variety of electrophilic species, especially with carbon electrophiles to form a new carbon—carbon bond. An electrophile enters on the terminus of the allylic system and the cleavage of the carbon—silicon bond occurs to give a new allylic system in which the double bond is relocated adjacent to its original position. Allylsilanes al...

Dicopper(i) complexes with the chelating dmapm ligand [dmapm = 1,1-bis{di(o-N,N-dimetylanilinyl)phosphino}methane] have been synthesized and characterized structurally. Synthesis of the acetonitrile adduct [Cu2(μ-dmapm)(CH3CN)2][BF4]2 () has been presented and the dicopper electrophile has been used as the starting material in reaction with Group 14 heteroborates. Coordination of the closo-bora...

New aryl- and heteroarylboronate esters chelated by dipropanolamine are synthesised directly from boronic acids. The corresponding anionic borates are readily accessible by deprotonation and demonstrate an increase in hydrocarbyl nucleophilicity in comparison to other common borates. The new borates proved competent for magnesium or zinc additive-free, direct boron-to-iron hydrocarbyl transmeta...