With
the
aim
to
design
new
water-soluble
organometallic
Ru(II)
complexes
acting
as
anticancer
agents
catalysing
transfer
hydrogenation
(TH)
reactions
with
biomolecules,
we
have
synthesized
four
monocarbonyl
(1-4)
featuring
1,4-bis(diphenylphosphino)butane
(dppb)
ligand
and
different
bidentate
nitrogen
(N^N)
ligands,
of
general
formula
[Ru(OAc)CO(dppb)(N^N)]n
(n
=
+1,
0;
OAc
acetate).
The
compounds
been
characterised
by
methods,
including
1H
31P
NMR
spectroscopy,
electrochemistry
well
single
crystals
X-ray
diffraction
in
case
1
4.
also
studied
for
their
hydrolysis
aqueous
environment,
catalytic
regioselective
reduction
NAD+
1,4-NADH
solution
sodium
formate
hydride
source.
Moreover,
stoichiometric
oxidation
investigated
UV-Visible
spectrophotometry
spectroscopy.
Overall,
initial
structure-activity
relationships
could
be
inferred
which
point
towards
influence
extension
aromatic
N^N
cationic
1-3
on
TH
both
reduction/oxidation
processes.
neutral
complex
4,
a
picolinamidate
ligand,
stands
out
most
active
catalyst
NAD+,
while
being
completely
inactive
NADH
oxidation.
compound
can
convert
pyruvate
into
lactate
presence
formate,
albeit
scarce
efficiency.
In
any
case,
all
compounds,
intermediates
observed
even
isolated
1-3.
Together,
insight
from
kinetic
electrochemical
characterization
suggests
that,
1-3,
sees
H-transfer
rate
limiting
step,
whereas
H-donor,
step
is
ruthenium
substrate.
latter
further
modulated
di-cationic
aquo-
or
mono-cationic
hydroxo-species
Instead,
stable
respect
solution,
appears
operate
via
mechanism.
Finally,
activity
ability
form
reactive
oxygen
species
(ROS)
cancerous
non-tumorigenic
cells
vitro.
Noteworthy,
conversion
aldehydes
alcohols
achieved
three
catalysts
living
cells,
assessed
fluorescence
microscopy.
Furthermore,
formation
intermediate
upon
treatment
cancer
cell
extracts
3
has
detected
this
study
paves
way
application
non-arene
based
biological
environment.
ACS Sustainable Chemistry & Engineering,
Год журнала:
2024,
Номер
12(16), С. 6206 - 6219
Опубликована: Апрель 9, 2024
The
present
study
addresses
the
challenges
in
catalytic
transfer
hydrogenation
using
methanol/ethanol
for
converting
biomass-derived
furanic
aldehydes
to
furfuryl
alcohols.
introduction
of
air-stable
Ru(II)-para-cymene
catalysts
with
imidazole-based
metal–ligand
cooperativity
represents
a
significant
advancement.
Spectroscopic,
situ
monitoring,
labeling,
and
DFT
investigations
reveal
mechanistic
details,
highlighting
role
Ru–H
generation
through
dehydrogenation
Ru(II)-alkoxide
intermediates.
Hydride
proton
transfers
are
facilitated
by
interconvertible
coordination
mode
imidazole
Ru(II)–para-cymene,
which
is
crucial
maintaining
catalyst's
efficiency
selectivity.
Notably,
pKa
N–H
coordinated
significantly
influences
reactivity,
following
specific
order
depending
on
attached
heterocycle:
>
pyridine
thiazole.
This
correlates
well
computed
activation
barrier
generation.
catalyst
exhibits
ease
synthesis,
stability
air
moisture,
use
renewable
hydrogen
sources,
excellent
selectivity
aldehydes,
applicability
various
potential
large-scale
processes.
These
features
collectively
contribute
economic
sustainable
nature
both
protocol,
providing
valuable
contribution
field
hydrogenation.
ACS Catalysis,
Год журнала:
2023,
Номер
13(16), С. 10798 - 10823
Опубликована: Авг. 1, 2023
With
the
aim
to
design
water-soluble
organometallic
Ru(II)
complexes
acting
as
anticancer
agents
catalyzing
transfer
hydrogenation
(TH)
reactions
with
biomolecules,
we
have
synthesized
four
monocarbonyl
(1–4),
featuring
1,4-bis(diphenylphosphino)butane
(dppb)
ligand
and
different
bidentate
nitrogen
(N∧N)
ligands,
of
general
formula
[Ru(OAc)CO(dppb)(N∧N)]n
(n
=
+1,
0;
OAc
acetate).
The
compounds
been
characterized
by
methods,
including
1H
31P
NMR
spectroscopies,
electrochemistry,
well
single-crystal
X-ray
diffraction
in
case
1
4.
also
studied
for
their
hydrolysis
an
aqueous
environment
catalytic
regioselective
reduction
nicotinamide
adenine
dinucleotide
(NAD+)
1,4-dihydronicotinamide
(1,4-NADH)
solution
sodium
formate
a
hydride
source.
Moreover,
stoichiometric
oxidation
1,4-NADH
investigated
UV–visible
spectrophotometry
spectroscopy.
results
suggest
that
cycle
can
start
directly
from
intact
compound
or
its
aquo/hydroxo
species
(in
1–3)
afford
ruthenium
complex.
Overall,
initial
structure–activity
relationships
could
be
inferred
which
point
toward
influence
extension
aromatic
N∧N
cationic
1–3
on
TH
both
reduction/oxidation
processes.
While
complex
3
is
most
active
NADH
O2,
neutral
4,
picolinamidate
ligand,
stands
out
catalyst
NAD+,
while
being
completely
inactive
oxidation.
convert
pyruvate
into
lactate
presence
formate,
albeit
scarce
efficiency.
In
any
case,
all
compounds,
intermediates
observed
even
isolated
1–3.
Together,
insights
kinetic
electrochemical
characterization
that,
1–3,
sees
H-transfer
rate-limiting
step,
whereas
NAD+
H-donor,
step
substrate,
suggested
density
functional
theory
(DFT)
calculations.
Compound
stable
respect
solution,
appears
operate
via
mechanism
other
derivatives.
Finally,
activity
ability
form
reactive
oxygen
(ROS)
cancerous
nontumorigenic
cells
vitro.
Noteworthy,
conversion
aldehydes
alcohols
achieved
three
catalysts
living
cells,
assessed
fluorescence
microscopy.
Furthermore,
formation
intermediate
upon
treatment
cancer
cell
extracts
has
detected
this
study
paves
way
application
non-arene-based
biological
environment.
Catalysts,
Год журнала:
2020,
Номер
10(2), С. 162 - 162
Опубликована: Фев. 1, 2020
The
reduction
of
ketones
through
homogeneous
transfer
hydrogenation
catalyzed
by
transition
metals
is
one
the
most
important
routes
for
obtaining
alcohols
from
carbonyl
compounds.
interest
this
method
increases
when
opportune
catalytic
precursors
are
able
to
perform
transformation
in
an
asymmetric
fashion,
generating
enantiomerically
enriched
chiral
alcohols.
This
reaction
has
been
extensively
studied
terms
catalysts
and
variety
substrates.
A
large
amount
information
about
possible
mechanisms
available
nowadays,
which
high
importance
development
systems
with
excellent
outcomes
conversion,
enantioselectivity
Turn
Over
Frequency.
On
other
side,
many
mechanistic
aspects
still
unclear,
especially
those
have
shown
only
moderate
performances
hydeogenation.
case
neutral
[RuCl2(η6-arene)(P)]
cationic
[Rh(PP)2]X
(X
=
anion;
P
PP
mono-
bidentate
phosphine,
respectively)
complexes.
Herein,
a
summary
known
Transfer
Hydrogenation
these
complexes
provided
continuous
focus
on
more
relevant
features.
Dalton Transactions,
Год журнала:
2020,
Номер
49(24), С. 8375 - 8388
Опубликована: Янв. 1, 2020
High
cytotoxic
and
antimetastatic
activities
against
anaplastic
thyroid
cancer
are
displayed
by
cationic
complexes
[RuX(CO)(dppb)(phen)]Y
(X
=
Y
OAc,
OPiv,
SAc,
NCS;
X
Cl
PF6).
Tetrahedron Green Chem,
Год журнала:
2023,
Номер
1, С. 100008 - 100008
Опубликована: Янв. 1, 2023
The
development
of
effective
methodologies
for
the
sustainable
production
chemicals
and
biofuels
from
lignocellulosic
biomass
has
attracted
immense
attention
scientific
community.
However,
it
is
challenging
due
to
highly
complex
nature
sources.
Over
past
few
decades,
numerous
reports
targeting
various
catalytic
transformation
reactions
highlighting
vital
role
catalysts
in
substrate
activation
product
selectivity
have
appeared
literature.
Through
this
perspective,
we
present
recent
advances
metal
complexes-based
molecular
catalysis
transforming
biomass-derived
5-hydroxymethylfurfural
(5-HMF)
furfural
(FAL)
industrially
important
chemicals,
materials,
pharmaceuticals,
biofuels.
This
article
focuses
on
5-HMF
FAL
involving
hydrogenation,
ring
opening,
hydrogenolysis,
oxidation,
amination
over
catalysts,
provide
insights
into
systems
explored
allied
areas.
