Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(25), P. 9332 - 9337
Published: June 15, 2021
Here
we
report
the
use
of
pulse
radiolysis
and
spectroelectrochemistry
to
generate
low-valent
nickel
intermediates
relevant
synthetically
important
Ni-catalyzed
cross-coupling
reactions
interrogate
their
reactivities
toward
comproportionation
oxidative
addition
processes.
Pulse
provided
a
direct
means
singly
reduced
[(dtbbpy)NiBr],
enabling
identification
rapid
Ni(0)/Ni(II)
process
taking
place
under
electrolysis
conditions.
This
approach
also
permitted
measurement
Ni(I)
rates
with
electronically
differentiated
aryl
iodide
electrophiles
(kOA
=
1.3
×
104–2.4
105
M–1
s–1),
an
elementary
organometallic
step
often
proposed
in
nickel-catalyzed
reactions.
Together,
these
results
hold
implications
for
number
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(3), P. 1857 - 1878
Published: Jan. 20, 2022
A
highly
selective
and
divergent
synthesis
enables
access
to
various
molecules
has
garnered
broad
interest
from
not
only
organic
chemists
but
also
medicinal
biologists
who
work
with
chemical
libraries.
Since
the
20th
century,
such
transformations
have
been
achieved
using
transition-metal-catalyzed
reactions,
in
which
choice
of
catalyst
or
ligand
crucially
affects
selectivity.
Over
past
several
decades,
photocatalysts
attracted
a
considerable
amount
attention
because
they
provide
additional
ways
control
reaction
intermediates
product
selectivity
via
electron
energy
transfer.
From
this
perspective,
we
highlight
recent
development
switchable
syntheses
photocatalysts,
are
difficult
achieve
classical
catalytic
transformations.
Progress in Nuclear Magnetic Resonance Spectroscopy,
Journal Year:
2022,
Volume and Issue:
129, P. 28 - 106
Published: Jan. 19, 2022
A
'principles
and
practice'
tutorial-style
review
of
the
application
solution-phase
NMR
in
analysis
mechanisms
homogeneous
organic
organometallic
reactions
processes.
This
345
references
summarises
why
spectroscopy
is
uniquely
effective
such
studies,
allowing
non-destructive,
quantitative
a
wide
range
nuclei
common
to
reactions,
providing
exquisite
structural
detail,
using
instrumentation
that
routinely
available
most
chemistry
research
facilities.
The
two
parts.
first
comprises
an
introduction
general
techniques
equipment,
guidelines
for
their
selection
application.
Topics
include
practical
aspects
reaction
itself,
monitoring
techniques,
data
acquisition
processing,
temporal
concentration
data,
titrations,
DOSY,
use
isotopes.
second
part
series
15
Case
Studies,
each
selected
illustrate
specific
approaches
discussed
part,
including
situ
(1/2H,
10/11B,
13C,
15N,
19F,
29Si,
31P),
kinetic
equilibrium
isotope
effects,
entrainment,
shifts,
isotopes
at
natural
abundance,
scalar
coupling,
(VTNA,
RPKA,
simulation,
steady-state),
stopped-flow
NMR,
flow
rapid
injection
pure
shift
dynamic
nuclear
polarisation,
1H/19F
DOSY
illumination
NMR.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(23), P. 8106 - 8125
Published: Jan. 1, 2023
This
tutorial
review
delves
into
the
unique
advantages
of
electrochemistry
in
context
asymmetric
catalysis,
first
providing
a
brief
introduction
to
electrosynthesis,
then
exploring
representative
case
studies
with
mechanistic
focus.
Journal of Energy Storage,
Journal Year:
2023,
Volume and Issue:
62, P. 106926 - 106926
Published: Feb. 27, 2023
Owing
to
its
high
theoretical
specific
energy
density,
low
cost,
abundance
and
environmental
friendliness,
the
rechargeable
Zn-Air
batteries
(ZAB)
are
becoming
most
prevalent
candidate
as
storage
devices
for
consumer
electronics,
electric
vehicles.
Nevertheless,
interaction
of
O2
a
fuel
with
components
ZAB
is
highly
challenging
practical
implementations
this
technology.
The
underlying
electrochemical
reactions
in
involving
multi-electron
transfer,
adsorption/evolution
O2,
dissolution
Zn
metal
electrolyte,
need
robust-electrocatalyst
stable
Zn/electrolyte
interface.
This
prominently
evokes
an
in-depth
study
electrocatalytic
occurring
at
electrode/electrolyte
interphases
well
physiochemical
features
membranes
ZAB.
Therefore,
review
provides
significant
insights
into
fundamentals
air
battery
system
terms
mechanism,
composition/structural
performance
relationship
different
components.
A
detailed
section
has
been
devoted
summarizing
evaluating
factors
including
power
polarization
curves,
columbic
efficiency
correlation
catalyst's
redox
activity
(Eonset,
Ehalf-way,
Jd)
device
parameters
(OCV,
Ohmic
losses,
Pmax).
Moreover,
representative
studies
in-situ/operando
characterizations
have
also
summarized
reveal
structural
stability,
reaction
kinetics,
formation
by-products,
morphological
evolution.
intriguing
advanced
ZABs
flexibility,
photo-recharge
ability,
economic
feasibility,
fast
charging,
improved
stability
hybrid
systems
particularly
discussed.
For
accomplishment
these
functionalities,
chemical
heterogeneity
modifications
materials
(electrode,
electrolyte
membranes)
electrical
conductivity,
reduced
barrier,
increased
reactive
surface
area,
mass
transport
behavior
nanoscale
anticipated.
material
survey
could
be
beneficial
development
modification
new
catalysts
field
electrocatalysis.
Additionally,
prospect
green
technology,
viability
sustainability
highlighted.
Lastly,
based
on
discussion
recent
achievements,
some
challenges
outlooks
maturing
technology
academic
level
industrial
scale
set
forth.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
53(2), P. 566 - 585
Published: Dec. 5, 2023
This
tutorial
review
explains
the
use
of
cyclic
voltammetry
and
chronoamperometry
to
interrogate
reaction
mechanisms,
optimize
electrochemical
reactions,
or
design
new
reactions.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(15), P. 8689 - 8699
Published: April 4, 2023
While
the
oxidative
addition
of
Ni(I)
to
aryl
iodides
has
been
commonly
proposed
in
catalytic
methods,
an
in-depth
mechanistic
understanding
this
fundamental
process
is
still
lacking.
Herein,
we
describe
a
detailed
study
using
electroanalytical
and
statistical
modeling
techniques.
Electroanalytical
techniques
allowed
rapid
measurement
rates
for
diverse
set
iodide
substrates
four
classes
catalytically
relevant
complexes
(Ni(MeBPy),
Ni(MePhen),
Ni(Terpy),
Ni(BPP)).
With
>200
experimental
rate
measurements,
were
able
identify
essential
electronic
steric
factors
impacting
through
multivariate
linear
regression
models.
This
led
classification
mechanisms,
either
three-center
concerted
or
halogen-atom
abstraction
pathway
based
on
ligand
type.
A
global
heat
map
predicted
was
created
shown
applicable
better
reaction
outcome
case
Ni-catalyzed
coupling
reaction.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(16), P. 9720 - 9785
Published: July 17, 2023
Endogenous
photosensitizers
play
a
critical
role
in
both
beneficial
and
harmful
light-induced
transformations
biological
systems.
Understanding
their
mode
of
action
is
essential
for
advancing
fields
such
as
photomedicine,
photoredox
catalysis,
environmental
science,
the
development
sun
care
products.
This
review
offers
comprehensive
analysis
endogenous
human
skin,
investigating
connections
between
electronic
excitation
subsequent
activation
or
damage
organic
biomolecules.
We
gather
physicochemical
photochemical
properties
key
examine
relationships
chemical
reactivity,
location
within
primary
biochemical
events
following
solar
radiation
exposure,
along
with
influence
on
skin
physiology
pathology.
An
important
take-home
message
this
that
photosensitization
allows
visible
light
UV-A
to
have
large
effects
skin.
The
presented
here
unveils
potential
causes
continuous
increase
global
cancer
cases
emphasizes
limitations
current
protection
approaches.
