In this article we describe an efficient approach for the synthesis of cyclic diaryliodonium salts. The method is based on benzyl alcohols as starting materials and consists of an Friedel-Crafts-arylation/oxidation sequence. Besides a deep optimization, particluar focusing on the choice and ratios of the utilized Bronsted-acids and oxidants, we explore the substrate scope of this transformation. We also discuss an interesting isomerism of cyclic iodonium salts substituted with aliphatic substituents at the bridge head carbon. <br>
<p>We
have re-evaluated the X40x10 benchmark for halogen bonding using conventional
and explicitly correlated coupled cluster methods. For the aromatic dimers at
small separation, improved CCSD(T)–MP2 “high-level corrections” (HLCs) cause
substantial reductions in the dissociation energy. For the bromine and iodine species,
(n-1)d subvalence correlation increases dissociation energies, and turns out to
be more important for noncovalent interactions than is generally realized. As
in previous studies, we find that the most efficient way to obtain HLCs is to
combine (T) from conventional CCSD(T) calculations with explicitly correlated
CCSD-F12–MP2-F12 differences.</p>
A key challenge in predicting the multiphase chemistry of aerosols and droplets is connecting reaction probabilities, observed in an experiment, with the kinetics of individual elementary steps that control the...
Modulating Chalcogen Bonding and Halogen Bonding Sigma‐Hole Donor Atom Potency and Selectivity for Halide Anion Recognition