Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(17), P. 10192 - 10280
Published: Aug. 8, 2024
Radical
C–H
functionalization
represents
a
useful
means
of
streamlining
synthetic
routes
by
avoiding
substrate
preactivation
and
allowing
access
to
target
molecules
in
fewer
steps.
The
first-row
transition
metals
(Ti,
V,
Cr,
Mn,
Fe,
Co,
Ni,
Cu)
are
Earth-abundant
can
be
employed
regulate
radical
functionalization.
use
such
is
desirable
because
the
diverse
interaction
modes
between
metal
complexes
species
including
addition
center,
ligand
complexes,
substitution
single-electron
transfer
radicals
hydrogen
atom
noncovalent
complexes.
Such
interactions
could
improve
reactivity,
diversity,
selectivity
transformations
allow
for
more
challenging
reactions.
This
review
examines
achievements
this
promising
area
over
past
decade,
with
focus
on
state-of-the-art
while
also
discussing
existing
limitations
enormous
potential
high-value
regulated
these
metals.
aim
provide
reader
detailed
account
strategies
mechanisms
associated
The Chemical Record,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 16, 2025
Abstract
Direct
methane
to
methanol
conversion
is
a
dream
reaction
in
industrial
chemistry,
which
takes
inspiration
from
the
biological
production
catalysed
by
monooxygenase
enzymes
(MMOs).
Over
years,
extensive
studies
have
been
conducted
on
this
topic
bioengineering
MMOs,
and
tailoring
methods
isolate
MMOs
active
form.
Similarly,
remarkable
achievements
noted
other
activation
strategies
such
as
use
of
heterogeneous
catalysts
or
molecular
catalysts.
In
review,
we
outline
metabolism
performed
methanotrophs
detail
latest
advancements
site
structures
catalytic
mechanisms
both
types
MMOs.
Also,
recent
progress
bioinspired
approaches
using
various
catalysts,
especially
first‐row
transition
metal
zeolites
mechanistic
insights
are
discussed.
addition,
complexes
“Periana
catalyst”
for
through
methyl
ester
formation
presence
strong
acids
also
detailed.
Compared
zeolites‐mediated
field,
utilisation
application
still
its
nascent
phase
further
research
required
overcome
limitations
these
effectively.
Applied Organometallic Chemistry,
Journal Year:
2025,
Volume and Issue:
39(3)
Published: Feb. 25, 2025
ABSTRACT
Formation
of
a
tridentate
mono‐basic
hydrazone‐quinoxalyl
ligand
was
done
through
condensation
quinoxalyl‐2‐carbohydrazide
with
2‐hydroxy‐1‐naphthaldehyde
(H
2
dip).
The
coordination
capability
H
dip
Ni
(II)
and
V
(IV)
ions
examined
at
molar
ratios
1:1
leading
to
the
synthesis
two
distinct
complexes,
Ni(dip)
VO(dip),
respectively.
chemical
structure
validated
by
many
spectroscopic
techniques.
characterization
included
carbon,
hydrogen,
nitrogen
elemental
analyses
assessments
magnetic
properties
conductivity
behavior.
inhibited
effects
(organic
molecules)
its
chelating
agents
on
constrained
proliferation
three
specific
bacterial/fungal
types,
beside
established
human
cancer
cell
lines,
have
been
evaluated
in
relation
structural
impact
VO(dip)
compared
their
free
research
aimed
determine
nature
influence
metal
chelates
binding
affinity
dip,
Ni(dip),
for
ct‐DNA,
that
is,
calf
thymus
DNA,
depending
viscometric/spectrophotometric
alterations
characters.
Furthermore,
assessment
constants
(13.12,
15.19,
14.88
×
10
7
mol
−1
dm
3
),
Gibbs
energy
(−40.21,
−44.51,
−45.01
kJ
chromism
modes
respectively,
used
examine
interaction
mechanisms
attributing
increased
ct‐DNA
comparison
dip.
antioxidant
potential
within
SOD
(superoxide
dismutase)
DPPH
(2,2‐diphenyl‐1‐picrylhydrazyl)
assays,
reporting
respectable
reactivity.
catalysts
represented
superior
catalytic
oxidative
activity
1,2‐cyclooctene
(unsaturated
hydrocarbons,
CyO)
using
hydrogen
peroxide
homogenous
manner.
At
80°C,
yield
percentage
selective
epoxy‐cyclooctane
(CyOO)
90%
after
h
93%
acetonitrile
(the
best
solvent)
disparity
optimum
actions
these
pertained
differences
electronegativity
Lewis's
acidity,
suggested
mechanistic
pathway.
Zeitschrift für Naturforschung B,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 13, 2025
Abstract
The
two
trans
-Ru
VI
complexes,
(Ph
4
P)
2
[
-O
RuCl
]·CH
Cl
(
1
)
and
[(Ph
3
N]
),
were
obtained
in
high
yields
by
direct
oxidation
of
·3H
O
with
NaIO
,
followed
treatment
KOH
cation
exchange
reactions.
crystal
structures
the
complexes
determined
single
X-ray
diffraction.
Complexes
both
crystallize
triclinic
space
groups
P
1‾
$\overline{1}$
a
=
9.9766(16),
b
11.0566(18),
c
12.566(2)
Å,
α
69.354(2),
β
77.228(2),
γ
82.328(2)°,
Z
for
complex
10.897(3),
12.402(4),
14.449(5)
110.395(4),
91.853(4),
98.500(4)°,
.
characterized
FT-IR,
H
NMR,
31
P{H}
UV/Visible
spectroscopies,
their
electrochemical
properties
also
investigated.
New Journal of Chemistry,
Journal Year:
2022,
Volume and Issue:
46(45), P. 21684 - 21694
Published: Jan. 1, 2022
Copper(
ii
)
complexes
of
tridentate
(N
2
O)
Schiff
base
ligands
as
efficient
catalysts
for
2-aminophenol
oxidation
to
2-aminophenoxazin-3-one
with
excellent
reaction
rates.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(12), P. 5509 - 5519
Published: March 12, 2024
Introduction
of
oxygen
into
aromatic
C–H
bonds
is
intriguing
from
both
fundamental
and
practical
perspectives.
Although
the
3d
metal-catalyzed
hydroxylation
arenes
by
H2O2
has
been
developed
several
prominent
researchers,
a
definitive
mechanism
for
these
crucial
transformations
remains
elusive.
Herein,
density
functional
theory
calculations
were
used
to
shed
light
on
established
reaction
benzene
with
H2O2,
catalyzed
[NiII(tepa)]2+
(tepa
=
tris[2-(pyridin-2-yl)ethyl]amine).
Dinickel(III)
bis(μ-oxo)
species
have
proposed
as
key
intermediate
responsible
reaction.
Our
findings
indicate
that
while
dinickel
dioxygen
can
be
generated
stable
structure,
it
cannot
serve
an
active
catalyst
in
this
transformation.
The
allowed
us
unveil
unprecedented
composed
six
main
steps
follows:
(i)
deprotonation
coordinated
(ii)
oxidative
addition,
(iii)
water
elimination,
(iv)
(v)
ketone
generation,
(vi)
tautomerization
regeneration
catalyst.
Addition
oxygen,
which
occurs
via
radical
mechanism,
turns
out
rate-determining
step
overall
This
study
demonstrates
critical
role
Ni-oxyl
such
transformations,
highlighting
how
unpaired
spin
value
positive
charges
Ni–O•
complex
affect
activation
barrier
addition.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 24, 2025
Herein,
we
investigate
the
effects
of
ligand
design
on
nuclearity
and
reactivity
metal–ligand
multiply
bonded
(MLMB)
complexes
to
access
an
exclusively
bimetallic
reaction
pathway
for
C–H
bond
functionalization.
To
this
end,
diiron
alkoxide
[Fe2(PhDbf)2]
(1)
was
treated
with
3,5-bis(trifluoromethyl)phenyl
azide
imido
complex
[Fe2(PhDbf)2(μ-NC8H3F6)]
(2a)
that
promotes
hydrogen
atom
abstraction
(HAA)
from
a
variety
O–H
containing
substrates.
A
bis(amide)
[Fe2(PhDbf)2(μ-NHC8H3F6)(NHC8H3F6)]
(3)
generated,
prompting
isolation
analogous
bridging
amide
terminal
[Fe2(PhDbf)2(μ-NHC8H3F6)(OC19H15)]
(4)
asymmetric
pyridine-bound
[Fe2(PhDbf)2(μ-NC8H3F6)(NC5H5)]
(6a).
We
found
6a
is
competent
toluene
amination,
indicating
effect
Lewis
base-enhanced
Mechanistic
investigations
suggest
reactive
intermediate
as
no
monometallic
species
detected
during
time
course
reaction.
