Nature Chemical Engineering,
Год журнала:
2024,
Номер
1(2), С. 180 - 189
Опубликована: Фев. 8, 2024
Abstract
We
design
a
modular
programmable
inert-atmosphere
Schlenkputer
(Schlenk-line
computer)
for
the
synthesis
and
manipulation
of
highly
reactive
compounds,
including
those
that
are
air
moisture
sensitive
or
pyrophoric.
Here,
to
do
this,
we
constructed
Schlenk
line
using
Chemputer
architecture
inertization
glassware
can
achieve
vacuum
pressure
1.5
×
10
−3
mbar,
integrated
range
automated
handling,
storage
isolation
compounds
at
sub-ppm
levels
O
2
H
O.
This
has
enabled
automation
common
organometallic
reaction
types
four
compounds:
[Cp
Ti
III
(MeCN)
]
+
,
Ce
{N(SiMe
3
)
}
B(C
6
F
5
{
Dipp
NacNacMg
I
which
variously
temperature,
pressure,
water
oxygen.
Automated
crystallization,
filtration
sublimation
demonstrated,
along
with
analysis
inline
nuclear
magnetic
resonance
sampling
ultraviolet–visible
spectroscopy.
Finally,
demonstrate
low-temperature
reactivity
down
−90
°C
as
well
safe
handling
quenching
alkali
metal
reagents
dynamic
feedback
from
an
in
situ
temperature
probe.
ACS Catalysis,
Год журнала:
2023,
Номер
13(3), С. 1649 - 1661
Опубликована: Янв. 12, 2023
The
electrochemical
dinitrogen
reduction
reaction
(NRR)
has
recently
gained
much
interest
as
it
can
potentially
produce
ammonia
from
renewable
intermittent
electricity
and
replace
the
Haber-Bosch
process.
Previous
literature
studies
report
Fe-
Mo-carbides
promising
electrocatalysts
for
NRR
with
activities
higher
than
other
metals.
However,
recent
understanding
of
extraneous
nitrogen
oxide
contaminations
have
challenged
previously
published
results.
Here,
we
critically
assess
performance
several
reported
by
implementing
a
strict
experimental
protocol
to
minimize
effect
impurities.
successful
synthesis
α-Mo2C
decorated
carbon
nanosheets,
nanoparticles,
θ-Fe3C
χ-Fe5C2
nanoparticles
was
confirmed
X-ray
diffraction,
scanning
transmission
electron
microscopy,
photoelectron
Mössbauer
spectroscopy.
After
performing
chronoamperometric
tests
synthesized
materials,
concentrations
varied
between
37
124
ppb
are
in
close
proximity
estimated
background
level.
Notwithstanding
impracticality
these
extremely
low
yields,
observed
did
not
originate
but
unavoidable
NO
x
These
findings
contradiction
earlier
show
that
carbide
materials
active
under
employed
conditions.
This
further
emphasizes
importance
order
distinguish
catalyst
false
positive.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(34), С. 18742 - 18747
Опубликована: Авг. 21, 2023
The
oxidative
addition
of
aryl
electrophiles
is
a
fundamental
organometallic
reaction
widely
applied
in
the
field
transition
metal
chemistry
and
catalysis.
However,
analogous
version
based
on
main
group
elements
still
remains
largely
underexplored.
Here,
we
report
ability
well-defined
organobismuth(I)
complex
to
undergo
formal
with
wide
range
electrophiles.
process
facilitated
by
reactivity
both
ground
excited
states
N,C,N-bismuthinidenes
upon
absorption
low-energy
red
light.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(25)
Опубликована: Апрель 13, 2024
Abstract
Inverse
sandwich
complexes
of
Yb
and
Sm
stabilized
by
a
bulky
β‐diketiminate
(BDI)
ligand
have
been
prepared:
(BDI)Ln(η
6
,η
‐C
H
)Ln(BDI);
Ln=lanthanide.
Coordinated
benzene
ligands
can
be
neutral,
di‐anionic
or,
often
controversially
discussed,
even
tetra‐anionic.
The
formal
charge
on
is
correlated
to
assignment
the
metal
oxidation
state
which
generally
poses
problem.
Herein,
we
take
advantage
structural
similarities
found
when
comparing
Ca
II
with
,
Sr
complexes.
In
this
work,
an
excellent
overlap
Ca/Yb
inverse
structures
but
striking
difference
for
Sr/Sm
pair.
much
shorter
Sm−N
Sm‐C
distances
are
strong
evidence
III
‐benzene
−4
‐Sm
assignment.
This
was
further
supported
NMR
spectroscopy,
magnetic
susceptibility,
reactivity
comprehensive
computational
investigation.
Nature Chemical Engineering,
Год журнала:
2024,
Номер
1(2), С. 180 - 189
Опубликована: Фев. 8, 2024
Abstract
We
design
a
modular
programmable
inert-atmosphere
Schlenkputer
(Schlenk-line
computer)
for
the
synthesis
and
manipulation
of
highly
reactive
compounds,
including
those
that
are
air
moisture
sensitive
or
pyrophoric.
Here,
to
do
this,
we
constructed
Schlenk
line
using
Chemputer
architecture
inertization
glassware
can
achieve
vacuum
pressure
1.5
×
10
−3
mbar,
integrated
range
automated
handling,
storage
isolation
compounds
at
sub-ppm
levels
O
2
H
O.
This
has
enabled
automation
common
organometallic
reaction
types
four
compounds:
[Cp
Ti
III
(MeCN)
]
+
,
Ce
{N(SiMe
3
)
}
B(C
6
F
5
{
Dipp
NacNacMg
I
which
variously
temperature,
pressure,
water
oxygen.
Automated
crystallization,
filtration
sublimation
demonstrated,
along
with
analysis
inline
nuclear
magnetic
resonance
sampling
ultraviolet–visible
spectroscopy.
Finally,
demonstrate
low-temperature
reactivity
down
−90
°C
as
well
safe
handling
quenching
alkali
metal
reagents
dynamic
feedback
from
an
in
situ
temperature
probe.
