Density Functional Theory (DFT) calculations were employed to investigate the structural characteristics, electronic properties, and nonlinear optical properties of Benzyne-Based Chromophores at B3LYP/6-31G(d,p) level. The effects on the hyperpolarizabilities of various donor and acceptor substituent (H, F, Cl, Br, Me, NH2, OH, NH3+, COOH, CHO, CN, NO,NO2 ) were studied. The results reveale...

5,8-Didehydroisoquinolinium ion, a para benzyne analogue, was generated in a Fourier transform ion cyclotron resonance mass spectrometer, and its reactivity toward various neutral reagents was examined. A direct comparison of the reaction kinetics of the para benzyne, a meta isomer, and analogous monoradicals, indicates that the para benzyne is a poorer electrophile but a more reactive radical ...

In situ generated benzyne reacts at room temperature with (triphos)Pt-CH3+ to form a five-coordinate π-complex (2) that is isolable and stable in solution. Thermolysis of 2 at 60 °C generates (triphos)Pt(o-tolyl)+ (3), which is the product of formal migratory insertion of CH3- onto the coordinated benzyne. The reaction of 2 with the acid Ph2NH2+ yields toluene at room temperature over the cours...

The ortho-benzyne diradical, o-C(6)H(4) has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments: o-C(6)H(4)+Delta--> products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix...

This report details the synthesis of several benzonorbornadienes by Diels--Alder cycloaddition of cyclopentadiene derivatives with substituted benzyne intermediates, which were generated by low-temperature metal--halogen exchange of halobenzenes. General conditions were developed, allowing synthesis of most benzonorbornadienes described herein at the multigram scale with isolated yields approac...

Insertion of benzene rings into the amide bond using the reactive intermediate benzyne is described. Aromatic amides undergo smooth insertion when treated with O-triflatophenyl silane benzyne precursors, producing versatile aminobenzophenone products in good to excellent yield. The process is entirely metal-free and has been exemplified on the synthesis of biologically active acridones and acri...

A new benzyne transformation is described that affords versatile biaryl structures without recourse to transition-metal catalysis or stoichiometric amounts of organometallic building blocks. Aryl sulfonamides add to benzyne upon fluoride activation, and then undergo an aryl Truce-Smiles rearrangement to afford biaryls with sulfur dioxide extrusion. The reaction proceeds under simple reaction co...

The kinetics and mechanisms of the reactions of o-benzyne with propargyl and benzyl radicals have been investigated computationally. The possible reaction pathways have been explored by quantum chemical calculations at the M06-2X/6-311+G(3df,2p)//B3LYP/6-311G(d,p) level and the mechanisms have been investigated by the Rice-Ramsperger-Kassel-Marcus theory/master-equation calculations. It was fou...

The structures of m-benzyne and its fluorinated derivative, tetrafluoro-m-benzyne, were investigated using coupled cluster methods including triple excitations [CCSD(T) and CCSDT], different reference wave functions (spin-restricted Hartree-Fock, spin-unrestricted Hartree-Fock, and Brueckner), and different basis sets [6-31G(d,p) and correlation-consistent valence triple-zeta (cc-pVTZ)]. The in...