Nanoscale,
Год журнала:
2023,
Номер
16(3), С. 1038 - 1057
Опубликована: Дек. 21, 2023
This
review
summarizes
the
recent
advances
of
heterogeneous
catalysts
for
catalytic
transfer
hydrogenation
using
CO
2
-derived
formic
acid
and
methanol
as
hydrogen
sources.
Nature Energy,
Год журнала:
2022,
Номер
7(5), С. 438 - 447
Опубликована: Май 19, 2022
Abstract
Efficient
hydrogen
storage
and
release
are
essential
for
effective
use
of
as
an
energy
carrier.
In
principle,
formic
acid
could
be
used
a
convenient
medium
via
reversible
CO
2
hydrogenation.
However,
noble
metal-based
catalysts
currently
needed
to
facilitate
the
(de)hydrogenation,
produced
during
is
generally
released,
resulting
in
undesirable
emissions.
Here
we
report
α
-amino
acid-promoted
system
hydrogenation
using
Mn-pincer
complex
homogeneous
catalyst.
We
observe
good
stability
reusability
catalyst
lysine
amino
at
high
productivities
(CO
hydrogenation:
total
turnover
number
2,000,000;
dehydrogenation:
600,000).
Employing
potassium
lysinate,
achieve
>80%
H
evolution
efficiency
>99.9%
retention
ten
charge–discharge
cycles,
avoiding
re-loading
steps
between
each
cycle.
This
process
was
scaled
up
by
factor
18
without
obvious
drop
productivity.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(11), С. 4386 - 4464
Опубликована: Янв. 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.
Abstract
Direct
asymmetric
hydrogenation
(AH)
and
transfer
(ATH)
are
among
the
most
efficient
approaches
to
produce
chiral
building
blocks.
Recently,
these
types
of
transformations
have
witnessed
a
shift
towards
use
molecular
catalysts
based
on
earth‐abundant
transition
metals
due
their
ready
availability,
economic
advantage,
novel
properties.
With
particular
regard
manganese,
catalyst
development
has
seen
both
efficiency
substrate
scope
in
AH
ATH
greatly
improved,
with
emergence
large
number
well‐defined
Mn‐complexes
employed
this
field.
The
reaction
includes
C=O
bonds,
reduction
C=N
bonds
reductive
C=C
bonds.
Herein,
our
survey
area
focuses
catalytic
activity
such
complexes,
versatility
routes
convert
substrates
target
molecules.
We
consider
collected
findings
article
will
be
helpful
reader
by
providing
an
insight
into
ligand
design,
thereby
aiding
future
development.
Moreover,
review
is
aimed
at
highlighting
remarkable
progress
made
last
seven
years
manganese
complexes
for
enantioselective
reduction.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(26)
Опубликована: Апрель 19, 2022
A
unique
family
of
chiral
peraza
N6
-macrocyclic
ligands,
which
are
conformationally
rigid
and
have
a
tunable
saddle-shaped
cavity,
is
described.
Utilizing
their
manganese(I)
complexes,
the
first
example
earth-abundant
transition
metal-catalyzed
asymmetric
formal
anti-Markovnikov
hydroamination
allylic
alcohols
was
realized,
providing
practical
access
to
synthetically
important
γ-amino
in
excellent
yields
enantioselectivities
(up
99
%
yield
98
ee).
The
single-crystal
structure
MnI
complex
indicates
that
manganese
atom
coordinates
with
dialkylamine
moiety
bidentate
fashion.
Further
DFT
calculations
revealed
five
six
nitrogen
atoms
ligand
were
engaged
multiple
noncovalent
interactions
Mn,
an
isopropanol
molecule,
β-amino
ketone
intermediate
via
coordination,
hydrogen
bonding,
and/or
CH⋅⋅⋅π
state,
showing
remarkable
role
macrocyclic
framework.
The
chemo-
and
stereoselective
semi-hydrogenation
of
alkynes
to
alkenes
is
a
fundamental
transformation
in
synthetic
chemistry,
for
which
the
use
precious
4d
or
5d
metal
catalysts
well-established.
In
mankind's
unwavering
quest
sustainability,
research
focus
has
considerably
veered
towards
3d
metals.
Given
their
high
abundancy
availability
as
well
lower
toxicity
noxiousness,
they
are
undoubtedly
attractive
from
both
an
economic
environmental
perspective.
Herein,
we
wish
present
noteworthy
groundbreaking
examples
diastereoselective
alkyne
embark
on
journey
through
first-row
transition
ACS Omega,
Год журнала:
2022,
Номер
7(42), С. 37008 - 37038
Опубликована: Окт. 11, 2022
In
recent
years,
many
manganese-based
homogeneous
catalytic
precursors
have
been
developed
as
powerful
alternatives
in
organic
synthesis.
Among
these,
the
hydrofunctionalizations
of
unsaturated
C–C
bonds
correspond
to
outstanding
ways
afford
compounds
with
more
versatile
functional
groups,
which
are
commonly
used
building
blocks
production
fine
chemicals
and
feedstock
for
industrial
field.
Herein,
we
present
an
account
Mn-catalyzed
alkenes
alkynes
main
objective
finding
mechanistic
tendencies
that
could
serve
a
platform
works
come.