Crystal Growth & Design,
Journal Year:
2023,
Volume and Issue:
23(4), P. 2661 - 2674
Published: March 23, 2023
The
simultaneous
binding
of
a
molecular
entity
through
two
interactions
is
frequently
pursued
recognition
mode
due
to
the
advantages
it
offers
in
securing
self-assembly.
Here,
we
report
how
planarity
benzothienoiodolium
(BTI)
cation
allows
for
preorganizing
plane
hydrogen,
halogen,
and
chalcogen
bonds
(HBs,
XBs,
ChBs,
respectively)
formed
by
phenyl
iodolium
iodine,
thienyl
sulfur.
Crystallographic
analyses
some
BTI
salts
show
this
interaction
coplanarity
enables
their
coupling
point
toward
single
anion
that
coordinated
via
supramolecular
heteroditopic
synthon
XB/HB
or
XB/ChB,
latter
observed
here
first
time.
These
synthons
adopt
Janus-like
arrangement
around
iodine.
information
suggests
act
synergistically,
e.g.,
when
resulting
unusually
short
ChBs
Determination
electrostatic
potential,
Bader's
quantum
theory
"atoms-in-molecules"
analysis,
natural
bond
orbital
investigations
give
on
nature
energetic
aspects
contacts
crystals.
ChemPlusChem,
Journal Year:
2023,
Volume and Issue:
88(10)
Published: Sept. 7, 2023
Kinetic
data
based
on
1
H
NMR
monitoring
and
computational
studies
indicate
that
in
solution,
pyrazole-containing
iodonium
triflates
silver(I)
triflate
bind
to
each
other,
such
an
interplay
results
the
decrease
of
total
catalytic
activity
mixture
these
Lewis
acids
compared
separate
catalysis
Schiff
condensation,
imine-isocyanide
coupling,
or
nucleophilic
attack
a
triple
carbon-carbon
bond.
Moreover,
kinetic
cooperation
with
prevention
decomposition
salts
during
reaction
progress.
XRD
study
confirms
coordinates
center
via
pyrazole
N
atom
produce
rare
example
pentacoordinated
trigonal
bipyramidal
dinuclear
complex
featuring
cationic
ligands.
Chemistry - An Asian Journal,
Journal Year:
2023,
Volume and Issue:
18(7)
Published: Feb. 20, 2023
Abstract
Co‐crystallization
of
180°‐orienting
σ‐hole‐accepting
tectons,
namely,
1,4‐diisocyanobenzene
(
1
)
and
1,4‐diisocyanotetramethylbenzene
2
),
with
such
homoditopic
halogen
bond
donors
as
1,4‐diiodotetrafluorobenzene
(1,4‐FIB)
4,4’‐diiodoperfluorobiphenyl
(4,4’‐FIBP)
afforded
co‐crystals
⋅
1,4‐FIB,
4,4’‐FIBP,
1,4‐FIB.
Their
solid‐state
structures
exhibit
1D‐supramolecular
arrangements,
which
are
based
on
poorly
explored
I⋅⋅⋅C
bonding;
this
study
is
the
first
in
supramolecular
assembly
utilizing
bonding
a
terminal
C
atom
was
performed.
The
use
potentially
tetrafunctional
σ‐hole
accepting
tetraiodoethylene
(TIE)
leads
to
architecture
higher
dimension,
3D‐framework,
observed
structure
TIE.
DFT
calculations,
used
characterize
situation,
revealed
that
non‐covalent
interactions
moderately
strong,
ranging
from
−4.07
TIE
−5.45
kcal/mol
NBO
analysis
disclosed
LP(C)→σ*
charge
transfer
effects
relevant
all
co‐crystals.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(12)
Published: Feb. 21, 2024
Abstract
The
experimentally
obtained
kinetic
data
has
indicated
the
existence
of
a
synergetic
cocatalytic
effect
provided
by
an
iodonium
salt
in
base‐catalyzed
Knoevenagel
condensation.
diphenyliodonium
triflate
serving
as
halogen
bond‐donating
Lewis
acid
provides
higher
than
zinc(II)
or
triflic
serving,
respectively,
metal
cation‐based
and
Brønsted
acid.
Such
remains
same
for
broad
scope
carbonyl
compounds
covering
aldehydes
featuring
electron‐withdrawing
electron‐donating
substituents,
well
ketone
involved
reaction.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
unknown
Published: June 15, 2024
Abstract
Sulfonium,
selenonium,
telluronium
triflates,
as
well
chloronium,
bromonium,
and
iodonium
triflates
have
been
examined
in
the
model
Schiff
condensation
chalcogen‐
halogen
bond
donating
organocatalysts,
respectively.
The
kinetic
data
indicated
that
catalytic
effect
of
salt
is
provided
via
decrease
enthalpy
activation
reaction,
whereas
–
unexpectedly
caused
by
value
entropy
activation.
In
addition,
it
was
experimentally
shown
activity
sulfonium
selenonium
salts
significantly
lower
than
chloronium
bromonium
salts,
but
latter
pair
species
less
stable
under
reaction
conditions
former
pair.
Chalconium
and
halonium
salts
catalyze
Schiff
condensation.
Kinetic
data
DFT
calculations
show
that
the
catalytic
activity
correlates
with
maximum
electrostatic
potential
on
σ-holes,
whereas
other
factors
are
less
significant.
ChemPhysChem,
Journal Year:
2022,
Volume and Issue:
24(1)
Published: Aug. 31, 2022
Cyclic
diaryliodonium
compounds
like
iodolium
derivatives
have
increasingly
found
use
as
noncovalent
Lewis
acids
in
the
last
years.
They
are
more
stable
toward
nucleophilic
substitution
than
acyclic
systems
and
markedly
acidic.
Herein,
this
higher
acidity
is
analyzed
explained
via
quantum-chemical
calculations
energy
decomposition
analyses.
Its
key
origin
change
levels
hybridization
of
iodine's
orbitals,
leading
to
both
favorable
electrostatic
interaction
better
charge
transfer.
Both
latter
seem
contribute
similar
fashion,
while
hydrogen
bonding
well
steric
repulsion
with
phenyl
rings
play
at
best
a
minor
role.
In
comparison
iodolium,
bromolium
chlorolium
less
acidic
lighter
halogen,
which
predominantly
based
on
charge-transfer
interactions.
Journal of Physical Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
38(3)
Published: Feb. 14, 2025
ABSTRACT
Halogen
bond
donors
are
recognized
as
electrophilic
catalysts
in
reactions
involving
carbonyl
compounds.
This
study
describes
an
unexpected
inhibition
of
the
Knoevenagel
condensation
by
catalyst.
To
elucidate
intricacies
mechanism,
overall
reaction
order
and
rate
constants
were
determined
using
1
H
NMR
spectroscopy,
further
experiments
with
different
nucleophiles
conducted.
The
findings
revealed
that
primary
is
attributed
to
a
substantial
acceleration
side
aldehyde
methanolysis,
which
hinders
formation
final
alkene
product.
