The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
unknown, С. 1 - 8
Опубликована: Дек. 17, 2024
Selectivity
is
an
essential
aspect
in
catalysis.
At
present,
the
improvement
of
selectivity
for
complex
reactions
with
multiple
pathways/products,
example
carbon
dioxide
reduction
reaction
(CO2RR),
can
usually
be
achieved
only
one
pathway/product.
It
still
a
challenge
to
reversibly
modulate
between
two
pathways
or
products
CO2RR
by
catalyst.
Here,
we
propose
reversible
modulation
via
spin
crossover.
By
employing
first-principles
calculations,
six
crossover
molecular
catalysts
are
found
among
17
kinds
transition
metal
embedded
porphyrin
derivatives
(ppy_TM),
where
changes
axial
ligand
configurations
switch
state
high
and
low
spin.
For
ppy_Os
ppy_Ru,
alteration
effectively
influence
CO2
into
either
formic
acid
monoxide
changing
relative
stability
key
intermediates
*COOH
*HCOO.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(16), С. 1921 - 1930
Опубликована: Апрель 7, 2023
Comprehensive
Summary
The
radical‐mediated
reductive
functionalization
of
aryl
halides
has
been
extensively
studied.
However,
the
related
intermolecular
1,2‐diarylation
alkenes,
using
as
radical
sources,
remains
unexplored.
Herein,
a
new
electrophotocatalytic
alkenes
is
reported
and
cyanoaromatics
to
produce
polyarylated
alkanes.
Using
synergistic
cathodic
reduction
visible‐light
photoredox
catalysis,
various
electron‐rich
electron‐deficient
are
combined
with
characterize
broad
substrate
scope,
excellent
functional
group
compatibility,
selectivity
this
reaction.
Mechanistic
investigations
reveal
that
reaction
may
proceed
via
process
initiated
by
generation
radicals
from
terminated
radical‐radical
coupling
cyanoaromatic
anions.
RSC Sustainability,
Год журнала:
2023,
Номер
1(9), С. 2180 - 2196
Опубликована: Янв. 1, 2023
As
the
global
energy
landscape
transitions
towards
a
more
diversified
mix,
with
electricity
and
hydrogen
constituting
half
of
final
consumption
by
2050,
focus
on
efficient
sustainable
production
intensifies.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(1), С. 476 - 486
Опубликована: Янв. 1, 2024
Alkyne
semihydrogenation
is
a
broadly
important
transformation
in
chemical
synthesis.
Here,
we
introduce
an
electrochemical
method
for
the
selective
of
terminal
alkynes
using
dihydrazonopyrrole
Ni
complex
capable
storing
H2
equivalent
(2H+
+
2e–)
on
ligand
backbone.
This
chemoselective
over
internal
or
alkenes.
Mechanistic
studies
reveal
that
concerted
and
Z-selective.
Calculations
support
ligand-based
hydrogen-atom
transfer
pathway
instead
hydride
mechanism,
which
commonly
invoked
transition
metal
hydrogenation
catalysts.
The
synthesis
proposed
intermediates
demonstrates
catalytic
mechanism
proceeds
through
reduced
formal
Ni(I)
species.
high
yields
alkene
products
without
over-reduction
oligomerization
are
among
best
reported
any
homogeneous
catalyst.
Furthermore,
metal–ligand
cooperative
hydrogen
enabled
with
this
system
directs
efficient
flow
H
atom
equivalents
toward
alkyne
reduction
rather
than
evolution,
providing
blueprint
applying
similar
strategies
wide
range
electroreductive
transformations.
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
highlights
organo-mediators
that
enable
electrochemical
reactions
via
outer-sphere
electron
transfer
(ET),
offering
advantages
such
as
availability,
tunability,
and
simplified
post-processing
compared
to
direct
electrolysis.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(31), С. 17103 - 17111
Опубликована: Июль 25, 2023
Hydrogenation
reactions
of
carbon-carbon
unsaturated
bonds
are
central
in
synthetic
chemistry.
Efficient
catalysis
these
classically
recourses
to
heterogeneous
or
homogeneous
transition-metal
species.
Whether
thermal
electrochemical,
C-C
multiple
bond
catalytic
hydrogenations
commonly
involve
metal
hydrides
as
key
intermediates.
Here,
we
report
that
the
electrocatalytic
alkyne
semihydrogenation
by
molecular
Ni
bipyridine
complexes
proceeds
without
mediation
a
hydride
intermediate.
Through
combined
experimental
and
theoretical
investigation,
disclose
mechanism
primarily
involves
nickelacyclopropene
resting
state
upon
binding
low-valent
Ni(0)
A
following
sequence
protonation
electron
transfer
steps
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(7)
Опубликована: Дек. 21, 2023
Abstract
Catalytic
hydrogenation
of
nitriles
represents
an
efficient
and
sustainable
one‐step
synthesis
valuable
bulk
fine
chemicals.
We
report
herein
a
molecular
cobalt
electrocatalyst
for
selective
hydrogenative
coupling
with
amines
using
protons
as
the
hydrogen
source.
The
key
to
success
this
reductive
reaction
is
use
electrocatalytic
approach
cobalt‐hydride
generation
through
sequence
cathodic
reduction
protonation.
As
only
electrons
(e
−
)
(H
+
redox
equivalent
source,
general
electrohydrogenation
protocol
showcased
by
highly
straightforward
various
functionalized
structurally
diverse
amines,
well
deuterium
isotope
labeling
applications.
Mechanistic
studies
reveal
that
electrogenerated
transfer
nitrile
process
rate‐determining
step.
Catalysts,
Год журнала:
2023,
Номер
13(3), С. 542 - 542
Опубликована: Март 8, 2023
Heteroatom-doped
porous
carbon
material
(H-PCM)
was
synthesized
using
Anacardium
occidentale
(cashew)
nut’s
skin
by
a
simple
pyrolysis
route.
The
resulting
H-PCM
thoroughly
characterized
various
analytical
techniques
such
as
field
emission
scanning
electron
microscopy
(FE-SEM)
with
energy-dispersive
X-ray
(EDX)
spectroscopy,
high-resolution
transmittance
(HRTEM),
diffraction
(XRD),
Raman
nitrogen
adsorption–desorption
isotherms,
photoelectron
spectroscopy
(XPS),
and
attenuated
total
reflectance
Fourier
transform
infrared
(ATR-FTIR)
spectroscopy.
obtained
results
strongly
demonstrated
that
the
exhibited
nature,
continuous
sponge-like
sheet-like
smooth
morphology,
moderate
degree
of
graphitization/crystallinity
oxygen-,
nitrogen-,
sulfur-containing
functionalities
in
matrix.
After
structural
confirmation,
as-prepared
has
used
sustainable
electrocatalyst
for
hydrogen
evolution
reaction
(HER)
because
metal-free
carbonaceous
catalysts
are
one
most
promising
candidates.
showed
excellent
HER
activities
lowest
Tafel
slope
75
mV
dec−1
durable
stability
0.5
M
H2SO4
aqueous
solution.
Moreover,
this
work
provides
versatile
effective
strategy
designing
electrocatalysts
from
cheapest
biowaste/biomass
large-scale
production
gas
through
electrochemical
water
splitting.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 4, 2025
MXenes,
a
family
of
two-dimensional
(2D)
materials
based
on
transition
metal
carbides
and
nitrides,
have
desirable
properties,
such
as
high
conductivity,
surface
area,
tunable
groups,
for
electrocatalysis.
Nitride
in
particular,
shown
excellent
electrocatalytic
performance
the
nitrogen
oxygen
reduction
reactions,
but
fundamental
understanding
how
their
structures
evolve
during
electrocatalysis
remains
unknown.
Equally
important
yet
unknown
is
effect
reactivity
lattice
vibrational
behavior
nitride
MXenes
resulting
implications
Here,
we
investigate
properties
titanium
relevant
solvents
using
confocal
Raman
spectroscopy.
We
found
that
modes
are
attenuated
polar
solvents,
which
revealed
through
alteration
scattering
solvents.
Contrary
to
remain
unchanged
nonpolar
like
hydrocarbons
due
inactivity
nitrogen.
this
unique
nitrides
because
characteristics
sulfides
unaffected
by
solvent
types.
However,
inclusion
into
carbide
structure
does
exhibit
Raman-solvent
similar
suggesting
replacing
carbon
with
affects
MXene–light
interactions.
demonstrated
proof-of-concept
utilizing
enhance
reaction
ammonia
production.
In
summary,
elucidate
demonstrate
tunability
MXene
via
atom
substitution,
turn
can
be
exploited
advance
applications
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(22), С. 4390 - 4419
Опубликована: Янв. 1, 2024
The
merger
of
organic
electrosynthesis
with
3d
transition-metal
catalysis
has
offered
huge
opportunities
for
modern
synthesis.
This
review
summarizes
the
key
advancements
in
this
direction
published
recent
two
years.
