European Journal of Inorganic Chemistry,
Journal Year:
2022,
Volume and Issue:
26(6)
Published: Dec. 8, 2022
Abstract
Multinuclear
porphyrin‐based
ruthenium(II)‐NNNN
complexes
were
efficiently
assembled
by
means
of
coordinatively
unsaturated
16‐electron
mononuclear
ruthenium(II)‐pyrazolyl‐imidazolyl‐pyridine
complex,
zinc(II)
meso
‐tetra(4‐pyridyl)‐porphyrin
(ZnTPyP),
and
4,4′‐linked
bipyridines.
The
resultant
multinuclear
(Ru
4
Ru
8
)
exhibited
exceptionally
high
catalytic
activity
at
as
low
0.008
mol
%
loading
for
the
transfer
hydrogenation
reaction
ketones
in
refluxing
2‐propanol,
reaching
up
to
99
yields
5.7×10
6
h
−1
TOFs.
Organometallics,
Journal Year:
2021,
Volume and Issue:
40(6), P. 792 - 803
Published: March 9, 2021
The
complex
[Cp*RuCl(COD)]
reacts
with
LH2Cl2
(L
=
bis(3-methylimidazol-2-ylidene))
and
LiBun
in
tetrahydrofuran
at
65
°C
furnishing
the
bis-carbene
derivative
[Cp*RuCl(L)]
(2).
This
compound
NaBPh4
MeOH
under
dinitrogen
to
yield
labile
dinitrogen-bridged
[{Cp*Ru(L)}2(μ-N2)][BPh4]2
(4).
ligand
4
is
readily
replaced
by
a
series
of
donor
molecules
leading
corresponding
cationic
complexes
[Cp*Ru(X)(L)][BPh4]
(X
MeCN
3,
H2
6,
C2H4
8a,
CH2CHCOOMe
8b,
CHPh
9).
Attempts
recrystallize
from
MeNO2/EtOH
solutions
led
isolation
nitrosyl
[Cp*Ru(NO)(L)][BPh4]2
(5),
which
was
structurally
characterized.
allenylidene
[Cp*Ru═C═C═CPh2(L)][BPh4]
(10)
also
obtained,
it
prepared
reaction
2
HC≡CC(OH)Ph2
60
°C.
Complexes
4,
6
are
efficient
catalyst
precursors
for
transfer
hydrogenation
broad
range
ketones.
dihydrogen
has
proven
particularly
effective,
reaching
TOF
values
up
455
h–1
loadings
0.1%
mol,
high
functional
group
tolerance
on
reduction
scope
aryl
aliphatic
ketones
alcohols.
Catalysis Science & Technology,
Journal Year:
2022,
Volume and Issue:
12(18), P. 5597 - 5603
Published: Jan. 1, 2022
Preparation
of
bis-aNHC
Ru
catalysts,
identification
formation
intermediates
and
application
in
transfer
hydrogenation
Oppenauer-type
oxidation,
observing
an
inversion
activity
appearing
to
be
dependent
on
steric
hindrance.
Organometallics,
Journal Year:
2022,
Volume and Issue:
41(6), P. 686 - 697
Published: March 10, 2022
Four
ruthenium(II)
complexes
of
the
motif,
cis-RuCl2[Ph2P(CH2)4PPh2](ampy-L)
and
trans-RuCl2[Ph2P(CH2)4PPh2](ampy-L)
(ampy
=
2-(aminomethyl)pyridine;
L
Cl
or
OMe),
were
synthesized
for
potential
catalytic
applications.
The
fully
characterized
using
NMR
spectroscopy,
UV–vis
X-ray
crystallography,
electrochemical
analyses.
trans-isomer
was
observed
to
undergo
isomerization
cis-isomer,
kinetic
studies
reaction
showed
that
subtle
changes
in
ampy-L
electron
density
did
not
impact
rate
trans-to-cis
isomerization.
To
probe
utility
these
toward
catalysis,
transfer
hydrogenation
reactions
performed
reduction
a
variety
ketones.
All
three
cis-complexes
high
rates
yields
ketone
hydrogenation.
IntechOpen eBooks,
Journal Year:
2021,
Volume and Issue:
unknown
Published: May 19, 2021
Over
the
past
few
decades,
Ru
catalyzed
transfer
hydrogenation
(TH)
and
asymmetric
(ATH)
reactions
of
unsaturated
hydrocarbons,
imine,
nitro
carbonyl
compounds
have
emerged
as
economic
powerful
tools
in
organic
synthesis.
These
are
most
preferred
processes
having
applications
synthesis
fine
chemicals
to
pharmaceuticals
due
safe
handling
these
do
not
require
hazardous
pressurized
H2
gas.
The
catalytic
activity
selectivity
complexes
were
investigated
with
a
variety
ligands
based
on
pincer
NHC,
cyclophane,
half-sandwich,
organophosphine
etc.
coordinate
center
proper
orientation
labile
group
replaced
by
H-source
(like
methanol,
isopropanol,
formic
acid,
dioxane,
THF),
which
facilitate
β-hydrogen
generate
metal
hydride
species
(Ru-H)
produce
desired
reduced
product.
This
chapter
describes
recent
advances
TH
ATH
homogeneous
heterogeneous
catalysts
different
ligand
environments
mechanistic
details
leading
their
sustainable
industrial
applications.
Processes,
Journal Year:
2024,
Volume and Issue:
12(7), P. 1413 - 1413
Published: July 6, 2024
Recently,
scientists
have
been
developing
sustainable
processes,
and
in
this
context,
mechanochemistry
is
commonly
associated
with
green
chemistry
for
its
ability
to
reduce
waste
generation
from
chemical
reactions.
The
well-known
acetate
complex,
diacetate
bis(triphenylphosphine)
ruthenium(II)
[Ru(OAc)2(PPh3)2],
a
versatile
precursor
preparing
active
complexes
several
catalytic
This
report
presents
an
efficient
straightforward
manual
grinding
protocol
the
synthesis
of
ruthenium
carboxylate
starting
commercially
available
[RuCl2(PPh3)3]
metal
carboxylates.
work
represents
novel
preliminary
investigation
into
precursors’
alternative
solventless
route
based
on
grinding.
To
our
knowledge,
first
time
[Ru(OAc)2(PPh3)2]
has
prepared
via
mechanochemical
procedure.
method
also
investigated
other
alkali
carboxylates
yields
ranging
30
80%
were
obtained.
A
comparison
sustainability
environmental
impact
between
conventional
solution
carried
out
using
E-factor
Mass
Productivity.
While
complex
MP
only
slightly
better
compared
solvent
(3
vs.
4
~6
5
MP),
benzoate
higher
results
found
(1
~4
10
MP).
Reaction Chemistry & Engineering,
Journal Year:
2022,
Volume and Issue:
8(1), P. 164 - 174
Published: Oct. 19, 2022
Pyrazolone
derived
Ru(
iii
)
complexes
were
synthesized
and
applied
as
catalysts
in
the
C–H
activation
reaction
of
α,β-unsaturated
carbonyl
compounds.
In
addition
to
Heck
type
coupling,
ethanol
mediated
ethoxylation
was
also
witnessed.
