An o-Phenylene Bridged Noninnocent Bis-Azopyridyl Ligand and Its Copper Complexes: Synthesis, Characterization of Electron Transfer Events, and Use of the Cu Complexes for Oxidation of Alcohols
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 14, 2025
In
this
report,
an
o-phenylene-bridged
tetradented
redox-noninnocent
bis-azopyridyl
ligand
[L]
and
its
copper
complexes
[1]
[2]
were
synthesized
characterized.
The
electron
transfer
events
of
[L],
as
well
[2],
characterized
by
single-crystal
X-ray
structure
determination,
various
spectroscopic
studies,
DFT
calculations.
While
[[L]Cu(II)Cl2]
has
unreduced
[[L]•-Cu(I)Cl]
contains
a
one-electron-reduced
[L]•-
,
which
is
antiferromagnetically
coupled
with
the
unpaired
spin
on
Cu(II).
Reduction
one
generated
complex
[2]•-,
remained
in
electronically
bistable
situation
form
valence
tautomers:
[2A]•-,
[[L]•-Cu(I)Cl]•-
[2B]•-,
[[L]2-Cu(II)Cl]•-.
Further
one-electron
reduction
[2]•-
mixture
Cu
complexes:
[2A]-,
[[L]2-Cu(I)]-
[2B]-,
[[L]3•-Cu(II)]-.
Complexes
examined
for
catalytic
oxidation
alcohols.
was
more
efficient
than
[1].
protocol
highly
versatile
both
primary
secondary
aromatic
aliphatic
Mechanistic
investigations
showed
that
[[L]•-Cu(I)OCH2Ph]•-
(A)
active
catalyst,
subsequently,
through
ligand-based
redox
events,
acted
catalyst
over
course
reaction.
Язык: Английский
Aerial Oxidation of Alcohols by an Amide and Imidazole Functionalized Bioinspired Cu‐Complex and Its Switching with N‐Oxides
ChemistrySelect,
Год журнала:
2025,
Номер
10(18)
Опубликована: Май 1, 2025
Abstract
In
this
work,
employing
an
imidazole
and
amide
functionalized
pincer
like
Cu(II)
complex
as
a
pre‐catalyst,
alcohol
oxidation
reaction
without
N‐oxide
is
explored.
This
was
very
active
for
the
of
benzyl
alcohol.
The
best
catalytic
activity
observed
with
1
mmol
alcohol,
4
mol%
20
KO
t
Bu
in
toluene
at
70
°C
24
h.
Both
primary
well
secondary
alcohols
were
successfully
oxidized.
It
found
that,
protocol
more
efficient
(5–12
h
time)
than
(∼24
h).
by
can
be
switched
N‐oxides
2,2,6,6‐tetramethylpiperidinyloxy
(TEMPOH)
9‐azabicyclo[3.3.1]nonane
N
‐Oxyl
(ABNOH).
mechanism
studied
UV–vis,
EPR
X‐ray
photoelectron
spectral
studies.
Thus,
versatile
showed
good
functional
group
tolerance
substitutions
on
aromatic
alcohols.
Aerial
oxygen
acted
sole
oxidant
cooperation
/
Cu(I)
redox
events.
exhibited
switchable
behavior
presence
N‐oxide.
Though
Cu‐complex
catalyzed
explored,
such
where
occurs
containing
inert
ligand
cocatalyst
scarce.
Язык: Английский
Dioxygen Controlled Chemodivergent Cross‐Coupling of Primary and Secondary Alcohols Using Noninnocent Azo Aromatic Complexes of Cobalt(II) as Catalysts
ChemCatChem,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 14, 2024
Abstract
Herein,
employing
pincer
like
cobalt
(II)
complexes
containing
redox
noninnocent
azo‐benzimidazole
ligand
a
switchable
and
chemodivergent
catalytic
cross‐coupling
of
primary
secondary
alcohols
is
reported.
The
reactions
are
environmentally
benign
atom
efficient.
It
liberates
water
hydrogen
gas
as
the
only
byproducts.
While
reaction
in
inert
condition
gives
alkylated
ketones,
presence
air
well
lower
temperature
base
loading
selectively
results
unsaturated
ketones.
Both
protocols
have
very
good
functional
group
tolerance.
Thus,
wide
range
substrates
been
found
to
be
effective
for
synthesis
ketones
via
dehydrogenative
alcohols.
Several
control
experiments
kinetic
studies
were
performed
elucidate
pathways.
Язык: Английский
Cu–ABNO Catalyst for the Synthesis of Quinolines and Pyrazines via Aerobic Double Dehydrogenation of Alcohols
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 28, 2024
In
this
report,
a
new
imidazole-
and
amide-functionalized
pincer-like
Cu(II)
complex
(1)
was
synthesized
characterized.
By
employing
1
9-azabicyclo[3.3.1]nonane
NH-Oxyl
(ABNOH),
catalytic
protocol
for
alcohol
oxidation
the
subsequent
oxidation-triggered
synthesis
of
quinolines
pyrazines
were
explored.
Alcohols
such
as
2-aminoaryl
alcohols
also
oxidized
efficiently.
As
carbonyls
from
2-arylaminobenzyl
secondary
are
synthons
quinolines,
we
explored
their
directly
alcohols.
The
quite
efficient
completed
reaction
in
only
∼5–10
h.
Combinations
(a)
primary
with
or
ketones
(b)
found
to
be
very
effective
quinolines.
successful
various
1,2-diols
1,2-diaminobenzenes
10
Mechanistic
investigations
showed
that
generated
acted
an
active
catalyst:
it
activated
O2
subsequently
cooperation
N-Oxyl
(ABNO•)
α-CH
hydrogen
coordinated
alkoxide.
Then,
Cu(II)/Cu(I)
reduction
led
formation
carbonyl
compounds,
which
via
successive
C–C/C–N
coupling
reactions
resulted
heterocycles
presence
KOtBu
1.
Язык: Английский
Redox Noninnocent Copper(I) Complex Where Metal Is a Spectator and Ligand Is an Actor in the Glaser Coupling Reaction of Alkynes
Inorganic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 28, 2024
An
extended
trisazo
dipyridyl
ligand,
Copper-Catalyzed C(sp3)–H Alkylation of Fluorene with Primary and Secondary Alcohols using Borrowing Hydrogen Method
Chemical Communications,
Год журнала:
2024,
Номер
60(74), С. 10144 - 10147
Опубликована: Янв. 1, 2024
Despite
the
limited
success
of
copper-catalyzed
alkylations,
(NNS)CuCl
proved
to
be
an
effective
catalyst
for
sp
Язык: Английский
Cobalt-Catalyzed Divergence in C(sp3)–H Functionalization of 9H-Fluorene: A Streamlined Approach Utilizing Alcohols
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(20), С. 15103 - 15116
Опубликована: Окт. 8, 2024
Sustainable
chemical
production
demands
the
creation
of
innovative
catalysts
and
catalytic
technologies.
While
development
coherent
robust
systems
using
earth-abundant
transition
metals
is
essential,
it
remains
a
significant
challenge.
Herein,
an
expedient
divergence
strategy
for
tandem
dehydrogenative
C(sp
Язык: Английский
Supported Nickel Nanoparticles as Catalyst in Direct sp3 C–H Alkylation of 9H‐Fluorene Using Alcohols as Alkylating Agent
Chemistry - An Asian Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 14, 2024
Abstract
Herein,
we
report
an
inexpensive
first‐row
transition
metal
Ni
heterogeneous
catalytic
system
for
the
C
sp
3
‐mono
alkylation
of
fluorene
using
alcohols
as
alkylating
agents
via
borrowing
hydrogen
strategy.
The
protocol
displayed
versatility
with
high
yields
desired
products
various
types
primary
alcohols,
including
aryl/hetero
aryl
methanols,
and
aliphatic
agents.
catalyst
NPs@N−C
was
synthesized
high‐temperature
pyrolysis
strategy,
ZIF‐8
sacrificial
template.
characterized
by
XPS,
HR‐TEM,
HAADF‐STEM,
XRD
ICP‐MS.
is
stable
even
in
air
at
room
temperature,
excellent
activity
could
be
recycled
5
times
without
appreciable
loss
its
activity.
Язык: Английский
Zn(II)-Stabilized Azo-Anion Radical-Catalyzed Dehydrogenative Synthesis of Olefins
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 16, 2024
Herein,
we
describe
a
Zn-catalyzed
atom-economical,
inexpensive,
and
sustainable
method
for
preparing
broad
spectrum
of
substituted
olefins
utilizing
alcohols
as
the
main
precursor.
Using
Zn(II)
complex
[ZnLCl2]
(1)
redox-noninnocent
ligand
2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline
(L),
various
(E)-olefins
were
prepared
in
good
yields
by
coupling
with
sulfones
aryl
cyanides
under
an
inert
atmosphere.
Under
aerial
atmosphere,
vinyl
nitriles
isolated
up
to
82%
yield
reacting
benzyl
presence
1.
Control
experiments
mechanistic
investigation
indicate
active
involvement
aryl-azo
electron
hydrogen
reservoir,
permitting
1
perform
promising
catalyst.
Язык: Английский