Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(33)
Published: June 22, 2023
Abstract
Die
stark
wachsende
Bedeutung
von
grünem
Wasserstoff
und
erneuerbaren
Kohlenstoffressourcen
als
Rohstoffbasis
für
nachhaltige
Wertschöpfungsketten
eröffnet
Raum
bahnbrechende
Innovationen
bei
chemischen
Produktionsprozessen.
Fluktuation
Variabilität,
die
mit
der
Versorgung
nicht‐fossilen
Energieträgern
Rohstoffen
einhergehen,
stellen
Katalysatoren
vor
viele
Herausforderungen,
um
daraus
resultierende
Dynamik
zu
bewältigen.
Allerdings
ergeben
sich
auch
neue
Möglichkeiten,
wenn
das
Katalysatordesign
auf
eine
Leistung
abzielt,
“adaptiv”
nicht
“aufgabenspezifisch”
ist.
In
diesem
Beitrag
schlagen
wir
vor,
Adaptivität
in
Katalyse
Grundlage
drei
wesentlichen
Eigenschaften
definieren,
nämlich
Reversibilität,
Rapidität
Robustheit
(
R
3
‐Regel).
Zur
Begründung
des
wissenschaftlichen
Konzepts
zur
Darstellung
seines
Potenzials
chemische
Energiekonversion
werden
vielversprechende
Designstrategien
ausgewählte
Beispiele
beschrieben.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(33)
Published: June 22, 2023
Abstract
The
rapidly
growing
importance
of
green
hydrogen
and
renewable
carbon
resources
as
essential
feedstocks
for
sustainable
chemical
value
chains
opens
room
disruptive
innovations
regarding
production
processes.
fluctuation
variability
associated
with
non‐fossil
energy
raw
material
supply
holds
many
challenges
catalysts
to
cope
the
resulting
dynamics.
However,
new
opportunities
also
arise
once
catalyst
design
starts
aim
at
performance
that
is
“adaptive”
rather
than
“task‐specific”.
In
this
Scientific
Perspective,
we
propose
define
adaptivity
in
catalysis
on
basis
three
properties
are
reversibility,
rapidity,
robustness
(
R
3
rule).
Promising
strategies
selected
examples
described
substantiate
scientific
concept
highlight
its
potential
conversion.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(36)
Published: June 27, 2022
An
adaptive
catalytic
system
that
provides
control
over
the
nitroarene
hydrogenation
network
to
prepare
a
wide
range
of
aniline
and
hydroxylamine
derivatives
is
presented.
This
takes
advantage
delicate
interplay
between
rhodium(III)
center
Lewis
acidic
borane
introduced
in
secondary
coordination
sphere
metal.
The
high
chemoselectivity
catalyst
presence
various
potentially
vulnerable
functional
groups
its
readiness
be
deployed
at
preparative
scale
illustrate
practicality.
Mechanistic
studies
density
theory
(DFT)
methods
were
used
shed
light
on
mode
functioning
elucidate
origin
adaptivity.
competition
for
interaction
with
boron
solvent
molecule
substrate
was
found
crucial
When
operating
THF,
reduction
stops
platform,
whereas
reaction
can
directed
platform
toluene.
It
is
a
great
challenge
to
construct
green
catalytic
system
for
the
reduction
of
nitro
compounds
corresponding
amines
under
mild
conditions.
Due
low
energy
red
light,
it
challenging
develop
photocatalytic
selective
nitroaromatics
aromatic
driven
by
light.
A
bimetallic
porphyrin
metal–organic
framework
(Bi-P(Co)MOF)
was
characterized
Fourier
transform
infrared
spectroscopy,
X-ray
diffraction,
transmission
electron
microscopy,
scanning
and
energy-dispersive
techniques.
The
constructed
photocatalyst
Bi-PMOF-Co
shows
excellent
activity
conversion
in
high
yields
with
NaBH4
as
reducing
agent
at
room
temperature
light
irradiation.
Moreover,
protocol
showed
functional
group
compatibility,
recyclability
demonstrated
five-cycle
tests.
Organometallics,
Journal Year:
2023,
Volume and Issue:
42(8), P. 732 - 744
Published: April 6, 2023
The
one-pot
reaction
between
ethylenediamine,
paraformaldehyde,
and
Ph2PH
or
tBu2PH
gave
a
new
diphosphine
compound
1,3-bis((diphenylphosphaneyl)methyl)imidazolidine
L1
1,3-bis((di-tert-butylphosphaneyl)methyl)imidazolidine
L2,
respectively,
in
excellent
yields.
Metalation
with
[NiCl2(DME)]
the
presence
of
KPF6
afforded
pincer
carbene
nickel
chloride
complexes
[(PhPCP)NiCl]PF6,
1,
[(tBuPCP)NiCl]PF6,
2,
by
simultaneous
double
C–H
bond
activations
methylene
protons.
1
2
PhSNa
both
neutral
five-
ionic
four-coordinate
thiolate
[(PhPCP)Ni(SPh)2],
3,
[(PhPCP)NiSPh]PF6,
4,
[(tBuPCP)NiSPh]PF6,
5,
depending
upon
stoichiometry.
Interestingly,
an
excess
NaBH4
hydride
complex
[(tBuPCP)NiH]PF6,
6.
Their
structures
were
confirmed
X-ray
diffraction
method.
Of
these,
only
3
4
are
efficient
catalysts
for
hydrosilylation
aldehydes,
ketones,
nitroarenes
to
give
primary,
secondary
alcohols,
aromatic
amines
using
PhSiH3
after
hydrolysis.
Aldehydes
containing
different
substituents
conjugated
bonds,
aliphatic,
heterocyclic
aldehydes
converted
alcohols
isolated
yields
0.5
mol
%
h
under
neat
conditions
at
room
temperature.
ketones
requires
heating
toluene
products
moderate
Eight
their
very
good
including
chemoselective
reductions.
poor
performance
suggests
that
bound
group
plays
key
role
mediating
these
reactions
possibly
via
metal–ligand
cooperation.
Preliminary
mechanistic
studies
indicated
formation
silyl
detected
19Si
NMR
method
H2
evolution
among
others.
For
nitroarene
reduction,
detection
intermediates
followed
catalytic
reduction
N-phenylhydroxylamine
aniline
direct
mechanism.
