Photoelectron spectra of carbonyls,carbonates, oxalates and esterification effects

Photoelectron spectra are reported for dimethyl carbonate, ethylene carbonate, oxalic acid, dimethyl oxalate and diethyl oxalate. These spectra are discussed on a composite molecule basis using CNDO/s computational data and many of the individual bands are identified. The differential effects of esterification on ionization energies are discussed briefly.     

Monomers,dimers, and tetramers of 1- and 2-naphthoic acids

The absorption and emission spectra of 1- and 2-naphthoic acids and a number of their derivatives have been investigated. The S₁, T₁, and S₀ energy levels of solvent H-bonded monomers and internally H-bonded dimers are affected by the type of H-bonding, by periinteractions, by steric factors provided by substituent groups, and by solvent effects. The excimer fluorescence of 1-naphthoic acid has been detected and is the sole fluorescece of the crystal; it is attributed to a tetrameric sandwich complex of two dimers. The 1-naphthoic acid crystal also exhibits delayed excimer flurescence of a triplet-triplet annihilative type.     

Copper activation of boronic acids: factors affecting reactivity

The generation of nucleophiles from the combination of aryl boronic acids and catalytic amounts of copper salt allows a reactivity distinct from other organometallic species, such as organolithiums or Grignard reagents. Here we examine how the electronic and steric properties of the boronic acid affect the formation of active nucleophiles and their subsequent reactivity with iminium‐type compounds, showing that electron‐rich substrates display reduced reactivity. Copyright © 2014 John Wiley & Sons, Ltd.     

Positional and conformational dependence of long-range interactions in 3,16- and 3,17-androstanediones

The 5- and 5-conformations of androstane, androstan-3-one, androstan-16-one, androstan-17-one, androstane-3,16-dione and androstane-3,17-dione have been calculated by the SCF MNDO method, using full geometry optimization, in order to assess the dependence of long-range electronic interactions of the carbonyl groups on their location and on the conformation of the steroid ring system.     

The niobium and tantalum riddle: gas-phase monocation reactions with pyrene and pyrene-D10

Metal monocation gas-phase reactions with pyrene (Py) have been investigated. Of those cations which bind Py by abstraction of two hydrogen atoms, there are two subgroups of which Nb⁺ and Ta⁺ are the most striking and puzzling representatives. The Ta⁺-like group binds three Py units consecutively, each by expulsion of two hydrogen atoms, whereas the Nb⁺ group binds four Py units; however, in this latter case, the second Py attachment occurs without the expulsion of any hydrogen. When perdeuterated Py-D₁₀ is used, the Ta⁺ group behavior is unaffected, but the Nb⁺ group now exhibits a considerable degree of Py attachment in which no deuterium atoms are lost in the first reaction step. We will attempt to explain this behavior by using the results of reactions of Nb⁺ and Ta⁺ with Py in a Fourier transform mass spectrometer (FTMS).     

Photoelectron Spectra of Carbonyls. Oxalyl Chloride,Ethyl Oxalyl Choride,Ethyl Oxamate and N,N-Dimethyl Ethyl Oxamate

Photoelectron spectra are reported for oxalyl chloride, ethyl oxalyl chloride, ethyl oxamate and N,N-dimethyl ethyl oxamate. The spectra are assigned using a composite molecule approach.