34504-47-7

Upstream product

• 544-25-2 cycloheptatriene cation 
• 108-88-3 toluene 
• 24400-15-5 dimethylchloronium 
• 71-43-2 benzene 
• 12597-63-6 (zinc)2⁽¹⁺⁾ cluster 

Relevant academic research and scientific papers

Absorption Spectra and Photochemical Rearrangement of Cycloheptatriene Cation to Toluene Cation in Solid Argon

The toluene and cycloheptatriene cations have been produced and trapped in solid argon by matrix photoionization techniques.Toluene experiments gave a photosensitive 430-nm absorption and weak 480-nm band, the cycloheptatriene studies yielded a broad 480-nm absorption and a weak 430-nm band; these matrix bands are slightly red shifted the photodissociation spectra (PDS) peaks for the corresponding parent cations.Visible photolysis in cycloheptatriene experiments decreased the 480-nm band and increased the 430-nm absorption, indicating that cycloheptatriene cation can be photochemically rearrnged to toluene cation.The toluene cation absorption bandwidth is more than an order of magnitude less in solid argon than in ICR experiments; this may be due to quenching excess vibrational energy in the ground-state ion by the matrix and / or a reduction in the rate of internal conversion from the excited-state ion in the matrix owing to rapid relaxation to lower vibrational levels of the excited state where the density of states for vibronic coupling is less.The reduced photolysis rate of toluene cation in the matrix is consistent with the latter point and a efficient removal of vibrational energy from the vibrationally excited ground-state ion resulting from internal conversion.

Solvent, Isotope, and Substituent Effects on the Bimolecular Electron Transfer Reaction between Chlorine Oxide and Benzenes

The rate of back electron transfer following photoexcitation of ground-state complexes between ClO and aromatic molecules in nitrile solvents is examined.Both solvent effects on a single molecular complex and a series of complexes within a single solvent are analyzed in terms of commonly used theoretical models.For a single molecular complex (ClO-benzene), the rate of back electron transfer decreases with decreasing solvent dielectric constant and is temperature independent.This indicates that the reaction rate decreases with increasing exothermicity, behavior consistent with that expected for reactions in the Marcus inverted region.Investigation of the dependence of the reaction rate on exothermicity using a series of substituted benzenes as acceptor molecules in a single solvent revealed increasing reaction rates with increasing driving force, opposite to that observed upon varying solvent.Studies of deuteration effects on the reaction rate constant suggest that the origin of these disparate predictions arises from the assumptions made in carrying out the data analysis on the series of donor-acceptor complexes studied.In particular, both the inner-sphere and outer-sphere contributions to the reorganization energy are not constant for the set of molecules studied.This study demonstrates the difficulty in extracting accurate information on the reaction exothermicity, reorganization energy, and electronic coupling from measured rate constants.

Gas phase studies of Zn+2, Ag+3, and Ag+5

Laser desorption from ZnO and AgO produces small bare metal cluster ions.Laser desorption from a ZnO/AgO mixture produces an enhancement of the silver cluster ion signal with complete suppression of the zinc signal.The chemistry of Zn2+ indicates IP(Zn2) = 9.0 +/- 0.2 eV and D0(Zn+ - Zn) = 0.56 +/- 0.2 eV.The reactivity of Zn2+ with alkenes and alcohols is characterized by displacement of a zinc atom and formation of Zn+ - B (B = alcohol, alkene).The silver cluster ions are produced with excess kinetic energy; however, collisional cooling is achieved by trapping the cluster ions in a static pressure of argon.Charge transfer reactions indicate IP ( Agn ) nL2+ (n = 3,5; L = sec-butylamine) reacts with sec-butylamine via deamination and dehydrogenation indicating D0g (AgnL2+ - butadiene) > 1.73 eV.

The gas phase reactivity of chloronium ions by high pressure mass spectroscopy

The reactions of CH3ClCH3+ (I) and CH3ClCH2Cl+ (II) with a range of bases have been studied in a high pressure ion source.Reactant ion monitoring has been used to obtain the relative reactivities.Transfer of CH3+ from I and CH2Cl+ from II are the only reactions observed with N- and O-containing bases.Following addition of CH2Cl+ from II, the lower alkyl aromatics (ArH) yield either ArHCH2Cl+ or the benzyl ions ArCH2+ and ArCHCl+ while CH3+ transfer leads only to ArHCH3+.The reactivities of the alkyl aromatics increase with increasing exothermicity (benzene --> mesitylene) and there is an increasingly negative temperature coefficient of reactivity in the same order.

Benzene and Alkylbenzene Cations: An Electron Spin Resonance Study

Exposure of solutions of benzene, toluene and the xylenes in fluorotrichloromethane solvent at 77 K to 60Co γ-rays gave the corresponding radical cations, identified by e.s.r. spectroscopy.Trends in the methyl proton hyperfine coupling constants for these and for alkene cations are discussed in terms of electron-transfer from the C-H ?-orbitals.

Visible Absorption Spectra and Two-Photon Photodissociation of Halobenzene Cations in Solid Argon

Matrix photoionization experiments with bromobenzene, chlorobenzene, and fluorobenzene precursors produced absorptions dur to bromobenzene cation at 505 +/- 5 nm, chlorobenzene cation at 470 +/- 2 nm, and fluorobenzene cation at 431 +/- 1 nm, respectively, in excellent agreement with gas-phase photodissociation and photoelectron spectra.Two-photon dissosiation of the bromobenzene cation in solid argon was affected by photolysis in the very strong visible n2 ->? charge-transfer electronic transition, as found in earlier gas-phase work.The lack of significant two-photon dissociation of fluorobenzene cation is attributed to lower oscillator strength for the ?->? transition corresponding to absorption of the first photon.