Organometallics,
Journal Year:
2021,
Volume and Issue:
40(9), P. 1213 - 1220
Published: April 20, 2021
The
catalytic
reduction
of
carbon
dioxide
is
a
process
growing
interest
for
the
use
this
simple
and
abundant
molecule
as
renewable
building
block
in
C1-chemical
synthesis
hydrogen
storage.
well-defined,
bench-stable
alkylcarbonyl
Mn(I)
bis(phosphine)
complex
fac-[Mn(CH2CH2CH3)(dippe)(CO)3]
[dippe
=
1,2-bis(diisopropylphosphino)ethane]
was
tested
an
efficient
selective
non-precious-metal
precatalyst
hydrogenation
CO2
to
formate
under
mild
conditions
(75
bar
total
pressure,
80
°C),
presence
Lewis
acid
co-catalyst
(LiOTf)
base
(DBU).
Mechanistic
insight
into
reaction
provided
by
means
density
functional
theory
(DFT)
calculations.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(7), P. 4259 - 4298
Published: Jan. 1, 2021
This
review
summarizes
the
concepts,
mechanisms,
drawbacks
and
challenges
of
state-of-the-art
catalysis
for
CO2
to
MeOH
under
mild
conditions.
Thoughtful
guidelines
principles
future
research
are
presented
discussed.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(15), P. 4973 - 4977
Published: Feb. 18, 2019
A
series
of
MnI
complexes
containing
lutidine-based
chiral
pincer
ligands
with
modular
and
tunable
structures
has
been
developed.
The
complex
shows
unprecedentedly
high
activities
(up
to
9800
TON;
TON=turnover
number),
broad
substrate
scope
(81
examples),
good
functional-group
tolerance,
excellent
enantioselectivities
(85-98
%
ee)
in
the
hydrogenation
various
ketones.
These
aspects
are
rare
earth-abundant
metal
catalyzed
hydrogenations.
utility
protocol
have
demonstrated
asymmetric
synthesis
a
variety
key
intermediates
for
drugs.
Preliminary
mechanistic
investigations
indicate
that
an
outer-sphere
mode
substrate-catalyst
interactions
probably
dominates
catalysis.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(33), P. 14267 - 14275
Published: July 24, 2020
The
widespread
crisis
of
plastic
pollution
demands
discovery
new
and
sustainable
approaches
to
degrade
robust
plastics
such
as
nylons.
Using
a
green
approach
based
on
hydrogenation,
in
the
presence
ruthenium
pincer
catalyst
at
150
°C
70
bar
H2,
we
report
here
first
example
hydrogenative
depolymerization
conventional,
widely
used
nylons
polyamides,
general.
Under
same
catalytic
conditions,
also
demonstrate
hydrogenation
polyurethane
produce
diol,
diamine,
methanol.
Additionally,
an
where
monomers
(and
oligomers)
obtained
from
process
can
be
dehydrogenated
back
poly(oligo)amide
approximately
similar
molecular
weight,
thus
completing
closed
loop
cycle
for
recycling
polyamides.
Based
experimental
density
functional
theory
studies,
propose
that
is
facilitated
by
metal–ligand
cooperativity.
Overall,
this
unprecedented
transformation,
albeit
proof
concept
level,
offers
toward
cleaner
route
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(11), P. 4386 - 4464
Published: Jan. 1, 2022
The
emerging
field
of
organometallic
catalysis
has
shifted
towards
research
on
Earth-abundant
transition
metals
due
to
their
ready
availability,
economic
advantage,
and
novel
properties.
In
this
case,
manganese,
the
third
most
abundant
transition-metal
in
Earth's
crust,
emerged
as
one
leading
competitors.
Accordingly,
a
large
number
molecularly-defined
Mn-complexes
been
synthesized
employed
for
hydrogenation,
dehydrogenation,
hydroelementation
reactions.
regard,
catalyst
design
is
based
three
pillars,
namely,
metal-ligand
bifunctionality,
ligand
hemilability,
redox
activity.
Indeed,
developed
catalysts
not
only
differ
chelating
atoms
they
possess
but
also
working
principles,
thereby
different
turnover
numbers
product
molecules.
Hence,
critical
assessment
molecularly
defined
manganese
terms
atoms,
reaction
conditions,
mechanistic
pathway,
significant.
Herein,
we
analyze
complexes
catalytic
activity,
versatility
allow
multiple
transformations
routes
convert
substrates
target
This
article
will
be
helpful
get
significant
insight
into
design,
aiding
design.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: Jan. 4, 2021
Abstract
Any
catalyst
should
be
efficient
and
stable
to
implemented
in
practice.
This
requirement
is
particularly
valid
for
manganese
hydrogenation
catalysts.
While
representing
a
more
sustainable
alternative
conventional
noble
metal-based
systems,
catalysts
are
prone
degrade
under
catalytic
conditions
once
operation
temperatures
high.
Herein,
we
report
highly
Mn(I)-CNP
pre-catalyst
which
gives
rise
the
excellent
productivity
(TOF°
up
41
000
h
−1
)
stability
(TON
200
000)
catalysis.
system
enables
near-quantitative
of
ketones,
imines,
aldehydes
formate
esters
at
loadings
as
low
5–200
p.p.m.
Our
analysis
points
crucial
role
activation
step
performance
system.
employing
alkoxide
bases
can
ultimately
provide
catalytically
competent
species
hydrogen
atmosphere,
Mn(I)
with
hydride
donor
promoters,
e.g.
KHBEt
3
,
dramatically
improves
eliminates
induction
times
associated
slow
activation.
Cell Reports Physical Science,
Journal Year:
2023,
Volume and Issue:
4(5), P. 101341 - 101341
Published: March 29, 2023
Polymers
have
become
an
indispensable
part
of
our
daily
lives,
and
today
we
produce
around
370
MT
plastic
per
year.
Only
about
20%
it
is
being
recycled,
the
rest,
80%,
unleashed
into
environment
without
appropriate
treatment.
This
calls
forth
evaluation
strategies
available
for
mitigating
menace
"after-use"
waste.
Various
approaches
evolved
over
a
decade
are
at
different
levels
development.
Plastic
depolymerization
upcycling
considered
some
most
prominent
long-term
solutions.
The
metal-catalyzed
waste
to
chemical
feedstocks
has
emerged
as
one
promising
ways
address
global
pollution.
Therefore,
this
review
aims
examine
methods,
notify
recent
progress,
pinpoint
current
gaps,
gauge
potential
strategy.
Both
homogeneous
heterogeneous
catalysts
been
reported
depolymerize
various
polymers
last
decade.
Considerable
advances
in
metal-mediated
polyolefins,
polyesters,
polycarbonates,
polyurethanes,
polyamides,
polyethers.
above
produces
monomers
or
intermediates,
which
can
be
used
again
polymerization
thus
brings
back
circularity.
overview
debates
usage
high
temperatures,
sophisticated
ligands,
expensive
metals,
stoichiometric
reagents,
etc.,
depolymerization.
Thus,
summarizes
understanding
fundamental
science
depolymerization,
remaining
scientific
challenges,
opportunities.