Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 8, 2024
Abstract
The
recent
discovery
of
frustrated
Lewis
pairs
(FLPs)
during
the
activation
small
molecules
has
inspired
extensive
research
across
full
span
chemical
science.
Owing
to
nature
weak
interactions,
it
is
experimentally
challenging
directly
observe
and
modulate
FLP
at
molecular
scale.
Here
we
design
a
boron
cluster
anion
building
block
(B
10
H
8
2−
)
organic
amine
cations
([NR
4
]
+
,
R=−CH
3
−C
2
5
as
prove
feasibility
controlling
their
interaction
in
electric
double
layer
(EDL)
via
an
electrochemical
strategy.
In
situ
single‐molecule
electrical
measurements
Raman
monitoring
B
−[NR
formed
positively
charged
Au(111)
electrode
surface,
contrast
free‐standing
near
or
below
potential
zero
charge
(PZC).
Furthermore,
this
chemistry
leads
shift
local
density
states
clusters
towards
E
F
for
enhancing
electron
transport,
providing
new
prototype
reversible
single‐cluster
switch
that
digitally
switches
upon
layer.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(9), P. 4741 - 4785
Published: Jan. 1, 2024
The
review
summarizes
advances
in
the
radical
chemistry
of
polyfluorinated
arenes
under
photocatalytic
conditions.
fluoroaryl
fragment
serves
as
enabling
motif
for
reaction
design
and
efficient
generation
reactive
intermediates.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Feb. 13, 2024
Several
renewable
energy
schemes
aim
to
use
the
chemical
bonds
in
abundant
molecules
like
water
and
ammonia
as
reservoirs.
Because
O-H
N-H
are
quite
strong
(>100
kcal/mol),
it
is
necessary
identify
substances
that
dramatically
weaken
these
facilitate
proton-coupled
electron
transfer
processes
required
for
conversion.
Usually
this
accomplished
through
coordination-induced
bond
weakening
by
redox-active
metals.
However,
difficult
with
earth's
most
metal,
aluminum,
because
of
its
redox
inertness
under
mild
conditions.
Here,
we
report
a
system
uses
aluminum
non-innocent
ligand
achieve
significant
levels
bonds.
The
multisite
manifold
described
here
points
ligands
design
element
open
chemistry
more
elements
periodic
table.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(8), P. 2375 - 2396
Published: Jan. 1, 2024
This
review
is
focused
on
the
chemistry
of
frustrated
Lewis
pairs
(FLPs)
with
alkynes
and
surveys
range
stoichiometric
catalytic
reactions
enabled
by
this
concept.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(10), P. 4862 - 4876
Published: Jan. 1, 2024
Here,
we
discuss
predicting
thermal
and
photoinduced
single-electron
transfer
(SET)
in
frustrated
Lewis
pairs
(FLPs)
characterizing
the
resulting
radical
pair.
We
then
extend
these
methods'
application
to
main-group
chemistry.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(34)
Published: June 3, 2024
This
review
article
describes
the
development
of
use
aluminum
compounds
in
chemistry
frustrated
Lewis
pairs
(FLPs)
over
last
14
years.
It
also
discusses
synthesis,
reactivity
and
catalytic
applications
intermolecular,
intramolecular
so-called
hidden
FLPs
with
phosphorus,
nitrogen
carbon
bases.
The
intrinsically
higher
acidity
compared
to
their
boron
analogs
opens
up
different
reaction
pathways.
results
are
presented
a
more
or
less
chronological
order.
is
shown
that
Al
react
variety
polar
non-polar
substrates
form
both
stable
adducts
reversibly
activate
bonds.
Consequently,
some
title
were
such
as
dimerization
alkynes,
hydrogenation
tert-butyl
ethylene
imines,
C-F
bond
activation,
reduction
CO
Chem,
Journal Year:
2024,
Volume and Issue:
10(9), P. 2901 - 2915
Published: June 27, 2024
The
synthesis
of
organochalcogenides
remains
a
valuable
area
research
due
to
their
widespread
biological
applications,
particularly
in
pharmaceuticals.
Herein,
our
study
details
the
B(C6F5)3-catalyzed
Csp2–H
functionalization
diverse
arenes,
heteroarenes,
and
pharmacophores
with
thiosuccinimides
or
selenosuccinimides,
providing
selective
access
chalcogenated
products.
This
protocol
enables
late-stage
chalcogenation
drug
molecules
such
as
anti-inflammatory
naproxen,
estrogen
steroid
hormone
estradiol
derivatives,
industrially
relevant
trifluoromethylthiolation
reaction.
Furthermore,
this
C–S
coupling
methodology
provides
facile
metal-free
route
synthesize
vortioxetine,
an
antidepressant
drug,
plethora
significant
organic
motifs.
Detailed
NMR,
EPR
analyses,
density
functional
theory
(DFT)
computational
studies
indicate
that
elongation
thiosuccinimide
N–S
bond
is
assisted
by
boron-centered
adduct,
which
then
leads
stable
ion
pair
arene.
analysis
shows
transient
radical
pair,
potentially
off-cycle
species,
not
directly
involved
catalytic
process.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 22, 2025
Frustrated
Lewis
pairs
(FLPs)
have
been
widely
utilized
as
useful
reagents
and
catalysts
for
activation
of
small
molecules
(SMs)
through
thermally
controlled
equilibrium
formation
FLP-SM
adducts.
Herein,
we
report
a
light-
heat-responsive
FLP
system
on-demand
fixation
ethylene.
The
realizes
capture
release
ethylene
orthogonally
triggered
by
visible
light
heat,
demonstrating
potential
utility
nonmetallic
environmentally
benign
method
separation
storage
applicability
to
other
alkenes
is
also
demonstrated.
Mechanistic
investigations
clarify
that
the
photoexcited
enables
stepwise
radical
addition
ethylene,
followed
skeletal
rearrangement
afford
FLP-ethylene
adduct,
which
undergoes
promoted,
concerted
retro-cycloaddition
free
FLP.
As
synthetic
application,
nonequilibrium,
selective
cis-to-trans
isomerization
cyclooctene
achieved
with
This
work
discloses
unique
photochemical
reactivity
application
FLPs,
leading
further
expansion
chemistry
into
chemical
science.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 24, 2025
The
oxidation
of
triphenylphosphine
by
perfluorinated
phenaziniumF
aluminate
in
difluorobenzene
affords
hexaaryl-1,2-diphosphonium
dialuminate
1.
Dication
12+
is
valence
isoelectronic
with
elusive
hexaphenylethane,
where
instead
the
formation
a
mixture
trityl
radical
and
Gomberg's
dimer
favored.
Quantum-chemical
calculations
combination
Raman/IR
spectroscopies
rationalize
stability
P-P
bonded
suggest,
akin
to
halogens,
facile
homolytic
as
well
heterolytic
scission.
Thus,
serves
surrogate
both
triphenylphosphorandiylium
dication
(Ph3P2+)
monocation
(Ph3P·+).
Treating
1
dimethylaminopyridine
(DMAP)
or
tBu3P
replaces
under
bond
Qualifying
superoxidant
(E
vs
Fc/Fc+
=
+1.44
V),
oxidizes
trimethylphosphine.
Based
on
halide
abstraction
experiments
(-BF4,
-PF6,
-SbCl6,
-SbF6)
deoxygenation
triethylphosphine
oxide,
triflate
anions
toluic
acid,
also
features
Lewis
superacidity.
controlled
hydrolysis
Hendrickson's
reagent,
which
itself
finds
broad
use
dehydration
agent.
Formally,
scission
occurs
diphenyldisulfide
(PhSSPh)
triple
bonds
benzo-
acetonitrile.
irradiation
light
cleaves
homolytically
generates
transient
cations,
engage
H-atom
CH
phosphoranylation.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: May 27, 2024
Nitroxides
find
application
in
various
areas
of
chemistry,
and
a
more
in-depth
understanding
factors
controlling
their
reactivity
with
metal
complexes
is
warranted
to
promote
further
developments.
Here,
we
report
on
the
effect
centre
Lewis
acidity
both
distribution
O-
N-centered
spin
density
2,2,6,6-tetramethylpiperidine-N-oxyl
(TEMPO)
turning
TEMPO
from
N-radical
mode
scavenger
metal-TEMPO
systems.
We
use
Et(Cl)Zn/TEMPO
model
reaction
system
tuneable
solid
state
solution.
Among
products,
unique
acid-base
adduct
Cl
