Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 16, 2025
Synthetic
access
toward
well-defined,
monomeric
s-block
metal
complexes
is
mired
with
chemical
challenges,
primarily
attributed
to
the
formation
of
homoleptic
promoted
by
Schlenk
equilibrium.
Ligand
redistribution
significantly
pronounced
for
heavier
metals,
such
as
calcium,
which
form
bischelate
readily
through
traditional
synthetic
routes
transmetalation,
amination,
and
ligand
exchange.
Mechanistic
investigation
each
these
phenoxyimine
(ONN)
ligands
was
explored
ascertain
fundamental
parameters
promote
formation.
Donor
effects
from
coordinated
solvent
proved
be
deleterious,
in
an
effort
circumvent
bischelation,
a
new
calcium
bisamide,
{Ca[N(SiMe3)2]2(diox)2}∞,
synthesized
characterized
coordination
polymer
unique
square
planar
geometry,
rarely
seen
group
2
complexes.
Amination
{Ca[N(SiMe3)2]2(diox)2}∞
found
shift
equilibrium
favor
heteroleptic
species,
allowing
characterization
calcium-amido
complexes:
[ONN1Ca-N(SiMe3)2]2(diox)
[ONN3Ca-N(SiMe3)2(diox)]∞.
Subsequent
studies
showed
that
exchange
isolated
dioxane
THF
notably
shortened
stability
complex
solution.
Although
steric
have
previously
been
regarded
key
stabilization
complexes,
it
equally
important
consider
donor
ability
achieve
longer-lived
heavy
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(10), С. 5054 - 5082
Опубликована: Янв. 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.
Electrochemical
nitrogen
reduction
reaction
(NRR)
to
ammonia
(NH3
)
using
renewable
electricity
provides
a
promising
approach
towards
carbon
neutral.
What's
more,
it
has
been
regarded
as
the
most
alternative
traditional
Haber-Bosch
route
in
current
context
of
developing
sustainable
technologies.
The
development
class
highly
efficient
electrocatalysts
with
high
selectivity
and
stability
is
key
electrochemical
NRR.
Among
them,
P-block
metal-based
have
significant
application
potential
NRR
for
which
possessing
strong
interaction
N
2p
orbitals.
Thus,
offers
good
NH3
.
density
state
(DOS)
near
Fermi
level
concentrated
catalysts,
indicating
ability
metal
active
sites
N2
adsorption
activation
by
donating
p
electrons.
In
this
work,
we
systematically
review
recent
progress
effect
on
activity,
are
discussed.
Specifically,
catalyst
design,
nature
some
strategies
boosting
performance,
mechanism,
impact
operating
conditions
unveiled.
Finally,
challenges
outlooks
proposed.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(37)
Опубликована: Июль 21, 2023
Abstract
The
activation
of
dinitrogen
(N
2
)
by
transition
metals
is
central
to
the
highly
energy
intensive,
heterogeneous
Haber–Bosch
process.
Considerable
progress
has
been
made
towards
more
sustainable
homogeneous
activations
N
with
d‐
and
f‐block
metals,
though
little
success
had
main
group
metals.
Here
we
report
that
reduction
a
bulky
magnesium(II)
amide
[(
TCHP
NON)Mg]
(
NON=4,5‐bis(2,4,6‐tricyclohexylanilido)‐2,7‐diethyl‐9,9‐dimethyl‐xanthene)
5
%
w/w
K/KI
yields
magnesium‐N
complex
[{K(
NON)Mg}
(μ‐N
)].
DFT
calculations
experimental
data
show
unit
in
reduced
2−
dianion,
via
transient
anionic
magnesium(I)
radical.
compound
readily
reductively
activates
CO,
H
C
4
,
reactions
which
it
acts
as
masked
dimagnesium(I)
diradical.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(19)
Опубликована: Фев. 6, 2023
Abstract
Dinitrogen
(N
2
)
activation
and
functionalization
is
of
fundamental
interest
practical
importance.
This
review
focuses
on
N
addition
to
unsaturated
substrates,
including
carbon
monoxide,
dioxide,
heteroallenes,
aldehydes,
ketones,
acid
halides,
nitriles,
alkynes,
allenes,
mediated
by
transition
metal
complexes,
which
afforded
a
variety
N−C
bond
formation
products.
Emphases
are
placed
the
reaction
modes
mechanisms.
We
hope
that
this
work
would
stimulate
further
explorations
in
challenging
field.
Sustainable Energy & Fuels,
Год журнала:
2024,
Номер
8(16), С. 3476 - 3495
Опубликована: Янв. 1, 2024
Flatland
materials
were
meticulously
surveyed
to
explore
their
functionality
in
photochemical
and
electrochemical
nitrogen
reduction
reaction
applications.
New
insights
are
presented
for
pilot-scale
NRR
operations
via
2D
materials.
Relay
overall
nitrogen
fixation
presents
an
intriguing
approach
to
the
simultaneous
production
of
nitric
acid
and
ammonia.
However,
it
remains
a
significant
challenge
due
manipulating
dual
active
sites
on
both
temporal
spatial
mesoscopic
scales.
In
this
study,
we
propose
bionic
seesaw
Bi4O5Cl2-Bi4O5Br2
heterojunction,
which
establishes
one-way
reaction
channel
through
entanglement
effect,
challenging
inherent
idea
synchronous
in
heterojunction.
Notably,
adaptive
interface
functions
as
fulcrum
by
incorporating
tensile
Bi-Cl
bonds
compressive
Bi-Br
while
also
inducing
localized
surface
lattice
distortion
Bi-O
sequentially
activate
sites.
Therefore,
unsaturated
dynamic
properties
trigger
structure
enhance
charge
exchange
molecular
polarization
N2
during
reduction,
thereby
creating
hydroxy-rich
environment
for
ammonia
oxidation
process.
Our
work
offers
novel
site
control
perspective
clarifies
processes.
