Macromolecules,
Journal Year:
2024,
Volume and Issue:
57(10), P. 4926 - 4936
Published: May 15, 2024
Ester
and
amide
enolates
are
important
propagating
species
in
organometallic-mediated
polymerization
of
polar
vinyl
monomers,
but
the
effects
transition
main
group
metallic
counterions
have
not
been
systematically
understood.
In
this
study,
various
metal
triflates
along
with
PPh3
used
to
catalyze
Lewis
pair
anionic
(LPAP)
or
radical
(LPRP)
(meth)acrylates
acrylamides,
elements
solvents
determine
dominant
propagation
mechanism.
Specifically,
LPAP
LPRP
proceed
using
early
late
triflates,
respectively,
organic
on-water.
The
elementary
reactions
PPh3/Fe(OTf)3
kinetically
investigated.
Notably,
follows
pseudo-second-order
kinetics
respect
monomer
concentration,
which
contributes
initiation
propagation,
whereas
PPh3/Sc(OTf)3
proceeds
pseudo-zero-order
kinetics.
This
indicates
that
react
unactivated
free
Sc-activated
LPAP.
study
demonstrates
triflate-based
pairs
can
generate
new
polymerizable
distinctive
reactivities.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 6, 2025
Herein,
we
report
the
isolation
of
pyridine
moiety-functionalized
SiNSi
pincer-based
bis-silylene
ligand
(1)
and
its
reactivity
toward
various
halide
precursors
(X
=
Br
I)
group
13
elements
(M
Al,
Ga,
In).
This
gave
us
straightforward
access
to
pincer-coordinated
cations
(2–7).
These
complexes
are
duly
characterized
by
single-crystal
X-ray
diffraction
studies,
multinuclear
magnetic
resonance
spectroscopy
(1H,
13C,
29Si),
high-resolution
mass
spectrometry
techniques.
Their
electronic
properties
were
further
analyzed
with
help
quantum
chemical
calculations.
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 28, 2025
ConspectusThe
discovery
of
reversible
hydrogenation
using
metal-free
phosphoborate
species
in
2006
marked
the
official
advent
frustrated
Lewis
pair
(FLP)
chemistry.
This
breakthrough
revolutionized
homogeneous
catalysis
approaches
and
paved
way
for
innovative
catalytic
strategies.
The
unique
reactivity
FLPs
is
attributed
to
base
(LB)
acid
(LA)
sites
either
spatial
separation
or
equilibrium,
which
actively
react
with
molecules.
Since
2010,
heterogeneous
FLP
catalysts
have
gained
increasing
attention
their
ability
enhance
performance
through
tailored
surface
designs
improved
recyclability,
making
them
promising
industrial
applications.
Over
past
5
years,
our
group
has
focused
on
investigating
strategically
modifying
various
types
solid
that
are
from
classic
FLPs.
We
explored
systematic
characterization
techniques
unravel
underlying
mechanisms
between
active
reactants.
Additionally,
we
demonstrated
critical
role
catalysts'
intrinsic
electronic
geometric
properties
promoting
formation
stimulating
synergistic
effects.
been
greatly
enhanced
by
use
advanced
such
as
synchrotron
X-ray
diffraction,
neutron
powder
photoelectron
spectroscopy,
extended
absorption
fine
structure,
elemental
mapping
scanning
transmission
electron
microscopy,
paramagnetic
resonance
diffuse-reflectance
infrared
Fourier
transform
solid-state
nuclear
magnetic
spectroscopy.
These
provided
deeper
insights
into
structural
systems
future
design
catalysts.Understanding
distribution
overlapping
orbitals
LA
LB
pairs
essential
inducing
operando
target
reallocation
external
stimuli.
For
instance,
silicoaluminophosphate-type
zeolites
weak
orbital
overlap,
adsorption
polar
gas
molecules
leads
heterolytic
cleavage
Alδ+–Oδ−
bond,
creating
unquenched
LA–LB
pairs.
In
a
Ru-doped
metal–organic
framework,
Ru–N
bond
can
be
polarized
metal–ligand
charge
transfer
under
light,
forming
Ru+–N–
activation
framework
represents
groundbreaking
innovation
expands
potential
existing
materials.
already
employing
chemistry
dynamically
generate
products
substrates,
complete
mechanistic
interpretation
requires
thorough
examination
surrounding
environment.
hydrogen
spillover
surfaces
improves
conversion
efficiency
suppressing
poisoning
at
metal
sites.
situ
H2–H2O
conditions
enable
production
organic
chemicals
excellent
activity
selectivity
new
bifunctional
via
By
highlighting
novel
featuring
induction
effects
selection
elucidate
reaction
mechanisms,
hope
this
Account
will
offer
strategies
designing
characterizing
research
community.
Dalton Transactions,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
New
developments
in
the
area
of
heavier
pnictogen-based
radicals
continue
to
be
reported,
along
with
small
molecule
reactivity
and
newly
discovered
catalytic
reactions.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 7, 2025
Constructing
chemical
bonds
under
green
sustainable
conditions
has
drawn
attention
from
environmental
and
economic
perspectives.
The
dissociation
of
(hetero)aryl-halide
is
a
crucial
step
most
arylations
affording
(hetero)arene
derivatives.
Herein,
we
summarize
the
(hetero)aryl
halides
activation
enabling
direct
(hetero)arylation
trapping
reagents
construction
highly
functionalized
(hetero)arenes
benign
conditions.
strategies
for
aryl
iodides
are
classified
into
(a)
hypervalent
iodoarene
followed
by
functionalization
thermal/photochemical
conditions,
(b)
aryl-I
bond
in
presence
bases
with/without
organic
catalysts
promoters,
(c)
photoinduced
presence/absence
organophotocatalysts,
(d)
electrochemical
direct/indirect
electrolysis
mediated
organocatalysts
mediators
acting
as
electron
shuttles,
(e)
electrophotochemical
redox-active
organocatalysts.
These
modes
result
exhibiting
diverse
reactivity
formal
cations/radicals/anions
aryne
precursors.
coupling
these
reactive
intermediates
with
leads
to
facile
selective
formation
C-C
C-heteroatom
bonds.
ecofriendly,
inexpensive,
functional
group-tolerant
offer
alternatives
transition
metal-based
catalysis.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(6), P. 1315 - 1315
Published: March 14, 2025
S-Aryl
glycosides
are
not
only
popular
glycosyl
donors
in
carbohydrate
chemistry
but
also
serve
as
valuable
tools
various
biological
studies,
which
has
brought
significant
attention
to
their
preparation.
However,
there
remains
a
pressing
need
for
greener
synthesis
methods
this
area.
In
response,
mild,
sustainable,
and
metal-
photocatalyst-free
electron
donor–acceptor
(EDA)-mediated
approach
synthesizing
using
1-thiosugar
aryl
thianthrenium
salt
was
developed.
Our
strategy
utilizes
the
donor,
overcoming
traditional
reliance
on
electron-rich
thiols,
such
or
carbonyl
typically
required
forming
EDA
complexes.
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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(29), P. 20425 - 20431
Published: July 8, 2024
p-Diarylboryl
halothiophenols
are
developed
and
unequivocally
characterized.
Their
photophysical
properties
catalytic
performance
unveiled
by
experimental
theoretical
investigations.
This
novel
class
of
triarylboranes
behaves
as
a
Brønsted
acid
to
generate
the
corresponding
borylthiophenolate
that
can
absorb
visible
light
undergo
intramolecular
charge
transfer
form
radical
pair
consisting
boron
anion
thiyl
radical,
which
acts
single-electron
reductant
while
engaging
in
hydrogen
atom
regenerate
parent
borylthiophenol.
The
synthetic
relevance
this
mode
action
is
demonstrated
establishment
unique
catalysis
integrates
three
different
yet
tunable
functions
single
cycle,
thereby
allowing
borylthiophenols
solely
promote
assembly
sterically
congested
1,2-diols
1,2-aminoalcohol
derivatives
via
radical–radical
cross-coupling.
