Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(35), P. 15004 - 15011
Published: Aug. 7, 2020
Reduction
of
dinitrogen
(N2)
is
a
major
challenge
for
chemists.
Cooperation
multiple
metal
centers
to
break
the
strong
N2
triple
bond
has
been
identified
as
crucial
step
in
both
industrial
and
natural
ammonia
syntheses.
However,
reports
cleavage
by
multimetallic
uranium
complex
remain
extremely
rare,
although
species
were
used
catalyst
early
Harber-Bosch
process.
Here
we
report
two
nitrides
uranium-rhodium
cluster
at
ambient
temperature
pressure.
The
nitride
product
further
reacts
with
acid
give
substantial
yields
ammonium.
presence
this
was
revealed
X-ray
crystallographic
computational
studies.
This
study
demonstrates
that
clusters
containing
transition
metals
are
promising
materials
fixation
reduction.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(36)
Published: July 5, 2022
The
electrocatalytic
nitrogen
reduction
reaction
(NRR)
on
metal-free
catalysts
is
an
attractive
alternative
to
the
industrial
Haber-Bosch
process.
However,
state-of-the-art
electrocatalysts
still
suffer
from
low
Faraday
efficiencies
and
ammonia
yields.
Herein,
we
present
a
molecular
design
strategy
develop
defective
boron
carbon
nitride
(BCN)
catalyst
with
abundant
unsaturated
B
N
atoms
as
Lewis
acid
base
sites,
which
upgrades
single
"Lewis
catalysis"
"frustrated
pairs
(FLPs)
catalysis."
14
N2
/15
exchange
experiments
density
functional
theory
(DFT)
calculations
reveal
that
FLPs
can
adsorb
molecule
form
six-membered
ring
intermediate,
enables
cleavage
of
via
pull-pull
effect,
thereby
significantly
reducing
energy
barrier
-0.28
eV.
Impressively,
BCN
achieves
high
efficiency
18.9
%,
yield
20.9
μg
h-1
mg-1cat.
,
long-term
durability.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(14), P. 5930 - 5973
Published: Jan. 1, 2022
Radical
species
are
significant
in
modern
chemistry.
Their
unique
chemical
bonding
and
novel
physicochemical
properties
play
roles
not
only
fundamental
chemistry,
but
also
materials
science.
Main
group
element
radicals
usually
transient
due
to
their
high
reactivity.
Highly
stable
often
stabilized
by
π-delocalization,
sterically
demanding
ligands,
carbenes
weakly
coordinating
anions
recent
years.
This
review
presents
the
advances
synthesis,
characterization,
reactivity
physical
of
isolable
main
radicals.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(16), P. 10468 - 10526
Published: Aug. 9, 2023
Heteroatom-centered
diradical(oid)s
have
been
in
the
focus
of
molecular
main
group
chemistry
for
nearly
30
years.
During
this
time,
diradical
concept
has
evolved
and
shifted
to
rational
design
specific
applications.
This
review
article
begins
with
some
important
theoretical
considerations
tetraradical
concept.
Based
on
these
considerations,
terms
ligand
choice,
steric,
symmetry,
electronic
situation,
element
reactivity
is
highlighted
examples.
In
particular,
heteroatom-centered
reactions
are
discussed
compared
closed-shell
such
as
pericyclic
additions.
The
comparison
between
reactivity,
which
proceeds
a
concerted
manner,
open-shell
stepwise
fashion,
along
diradical(oid)
design,
provides
understanding
interesting
unusual
class
compounds.
application
diradical(oid)s,
example
small
molecule
activation
or
switches,
also
highlighted.
final
part
application-related
details
spectroscopy
followed
by
an
update
tetraradical(oid)s
published
last
10
years
since
2013.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(8), P. 3896 - 3951
Published: Jan. 1, 2024
This
review
provides
an
overview
of
main
group
carbene
analogues,
covering
recent
advancements,
synthesis
strategies,
and
the
diverse
reactivity
elements
in
groups
13–15
based
on
their
structural
characteristics.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(10), P. 5054 - 5082
Published: Jan. 1, 2024
This
review
summarises
advances
in
the
chemistry
of
low-oxidation
state
and
hydrido
group
2
metal
complexes,
focussing
on
their
use
for
reductive
activation
feed-stock
gaseous
small
molecules,
subsequent
transformation
into
value
added
products.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 16, 2025
The
first
bottleable
example
of
a
neutral
Group
13
atom
bound
only
by
donor
ligands
(L)
has
been
fully
characterized
spectroscopic
methods
and
its
structure
determined
single-crystal
X-ray
diffraction
study.
A
two-coordinate
paramagnetic
L2B0
complex
can
readily
be
accessed
through
facile
reduction
reaction
is
stabilized
π-accepting
cyclic
(alkyl)(amino)carbene
(CAAC)
ligands.
Further
(CAAC)2B
leads
to
the
isolation
stable
diamagnetic
boride
anion.
In
turn,
oxidation
putative
formation
transient
cationic
borylene,
which
trapped
form
boron(I)
complex.
Density
functional
theory
calculations
support
formulation
as
boron(0)
strong
multiple
bonding.
Journal of the American Chemical Society,
Journal Year:
2019,
Volume and Issue:
142(1), P. 308 - 317
Published: Dec. 16, 2019
Boron
nitride
(BN),
with
outstanding
stability
and
robustness
in
diverse
polymorphs,
possesses
many
advantageous
properties
for
industrial
applications.
Activation
of
BN
materials
nonmetal
catalysts
is
among
the
most
revolutionary
challenging
tasks.
Taking
advantage
quantum
size
effect
synergistic
effect,
here
we
exploit
boron
nanotubes
(BNNTs)
encapsulating
early
transition
metal
nanowires,
which
experimentally
feasible,
nitrogen
fixation
ammonia
synthesis.
Using
first-principles
calculations
microkinetic
modeling,
show
that
coexisting
occupied
unoccupied
p
states
B
atoms
filled
BNNTs
can
effectively
mimic
d
metal.
They
act
as
electron
reservoirs
tunable
orbital
energies
occupancy,
are
beneficial
associative
N2
adsorption
hydrogenation.
Due
to
competition
between
thermodynamics
gas
kinetics
hydrogenation
reaction,
activity
be
optimized
by
controlling
type
filler
nanotube,
achieving
a
turnover
frequency
competitive
benchmark
Fe
catalyst.
These
results
manifest
universal
strategy
activating
nanomaterials
promising
family
robust
efficient
provide
vital
insights
into
activity-band
structure
relationship
p-block
catalysts.
