Solvent as Electron Donor: Donor/Acceptor Electronic Coupling Is a Dynamical Variable

Solvent as Electron Donor: Donor/Acceptor Electronic Coupling Is a Dynamical Variable

A study of diketopiperazines as electron-donor initiators in transition metal-free haloarene-arene coupling.

Several diketopiperazines have been shown to promote carbon-carbon coupling between benzene and aryl halides in the presence of potassium tert-butoxide and without the assistance of a transition metal catalyst. The structure of the diketopiperazine has an influence on its reductive potential and can help to promote the coupling of the more challenging aryl bromides with benzene.

Electron Transfer and Solvent-Mediated Electronic Localization in Molecular Photocatalysis.

This work provides a detailed mechanism for electron transfer in a heterodinuclear complex designed as a model system in which to study homogeneous molecular photocatalysis. With efficient Born-Oppenheimer molecular dynamics simulations, we show how intermediate, charge-separated states can mediate the electron transfer. We observe how Jahn-Teller distortion effects play out in solution, when t...

How membrane permeation is affected by donor delivery solvent.

We investigate theoretically and experimentally how the rate and extent of membrane permeation is affected by switching the donor delivery solvent from water to squalane for different permeants and membranes. In a model based on rate-limiting membrane diffusion, we derive explicit equations showing how the permeation extent and rate depend mainly on the membrane-donor and membrane-receiver part...

An Ab Initio Study of Specific Solvent Effects on the Electronic Coupling Element in Electron Transfer Reactions

An ab initio study of specific solvent effects on the electronic coupling element in electron transfer reactions. Specific solvent effects on the electronic coupling element for electron transfer are examined using two model donor–acceptor systems (Zn 2 ϩ and Li 2 ϩ) and several model ''solvent'' species (He, Ne, H 2 O, and NH 3). The effects are evaluated relative to the given donor–acceptor p...