Chemical Society Reviews,
Год журнала:
2022,
Номер
51(14), С. 5930 - 5973
Опубликована: Янв. 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.
Science,
Год журнала:
2023,
Номер
380(6650), С. 1147 - 1149
Опубликована: Июнь 15, 2023
The
complex
diberyllocene,
CpBeBeCp
(Cp,
cyclopentadienyl
anion),
has
been
the
subject
of
numerous
chemical
investigations
over
past
five
decades
yet
eluded
experimental
characterization.
We
report
preparation
and
isolation
compound
by
reduction
beryllocene
(BeCp2)
with
a
dimeric
magnesium(I)
determination
its
structure
in
solid
state
means
x-ray
crystallography.
Diberyllocene
acts
as
reductant
reactions
that
form
beryllium-aluminum
beryllium-zinc
bonds.
Quantum
calculations
indicate
parallels
between
electronic
diberyllocene
simple
homodiatomic
species
diberyllium
(Be2).
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.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(8), С. 4408 - 4413
Опубликована: Фев. 14, 2023
The
reactions
of
anionic
aluminium
or
gallium
nucleophiles
{K[E(NON)]}2
(E
=
Al,
1;
Ga,
2;
NON
4,5-bis(2,6-diisopropylanilido)-2,7-ditert-butyl-9,9-dimethylxanthene)
with
beryllocene
(BeCp2)
led
to
the
displacement
one
cyclopentadienyl
ligand
at
beryllium
and
formation
compounds
containing
Be-Al
Be-Ga
bonds
(NON)EBeCp
3;
4).
bond
in
beryllium-aluminyl
complex
[2.310(4)
Å]
is
much
shorter
than
that
found
small
number
previous
examples
[2.368(2)
2.432(6)
Å],
quantum
chemical
calculations
suggest
existence
a
non-nuclear
attractor
(NNA)
for
interaction.
This
represents
first
example
NNA
heteroatomic
interaction
an
isolated
molecular
complex.
As
result
this
unusual
electronic
structure
similarity
Pauling
electronegativities
aluminium,
charge
center
(+1.39)
3
calculated
be
less
positive
(+1.88).
distribution
suggests
possibility
nucleophilic
behavior
correlates
observed
reactivity
N,N'-diisopropylcarbodiimide─the
electrophilic
carbon
carbodiimide
undergoes
attack
by
beryllium,
thereby
yielding
beryllium-diaminocarbene
Nature Chemistry,
Год журнала:
2024,
Номер
16(8), С. 1295 - 1300
Опубликована: Май 17, 2024
Owing
to
its
high
toxicity,
the
chemistry
of
element
number
four,
beryllium,
is
poorly
understood.
However,
as
lightest
elements
provide
basis
for
fundamental
models
chemical
bonding,
there
a
need
greater
insight
into
properties
beryllium.
In
this
context,
homo-elemental
Be-Be
bond
interest.
Here
ligand
metathesis
diberyllocene
(1;
CpBeBeCp)-a
stable
complex
with
bond-has
been
investigated.
These
studies
yield
two
complexes
bonds:
Cp*BeBeCp
(2)
and
[K{(HCDippN)
Molecules,
Год журнала:
2024,
Номер
29(11), С. 2451 - 2451
Опубликована: Май 23, 2024
Magnesium-based
hydrogen
storage
materials
have
garnered
significant
attention
due
to
their
high
capacity,
abundance,
and
low
cost.
However,
the
slow
kinetics
desorption
temperature
of
magnesium
hydride
hinder
its
practical
application.
Various
preparation
methods
been
developed
improve
properties
magnesium-based
materials.
This
review
comprehensively
summarizes
recent
advances
in
materials,
including
mechanical
ball
milling,
methanol-wrapped
chemical
vapor
deposition,
plasma-assisted
organic
ligand-assisted
synthesis,
other
emerging
methods.
The
principles,
processes,
key
parameters,
modification
strategies
each
method
are
discussed
detail,
along
with
representative
research
cases.
Furthermore,
advantages
disadvantages
different
compared
evaluated,
influence
on
is
analyzed.
application
potential
these
also
assessed,
considering
factors
such
as
performance,
scalability,
cost-effectiveness.
Finally,
existing
challenges
future
directions
this
field
outlined,
emphasizing
need
for
further
development
high-performance
cost-effective
clean
energy
applications.
provides
valuable
insights
references
researchers
working
advanced
technologies.
ACS Organic & Inorganic Au,
Год журнала:
2024,
Номер
4(5), С. 432 - 470
Опубликована: Авг. 7, 2024
In
recent
years,
mechanochemistry
has
become
an
innovative
and
sustainable
alternative
to
traditional
solvent-based
synthesis.
Mechanochemistry
rapidly
expanded
across
a
wide
range
of
chemistry
fields,
including
diverse
organic
compounds
active
pharmaceutical
ingredients,
coordination
compounds,
organometallic
complexes,
main
group
frameworks,
technologically
relevant
materials.
This
Review
aims
highlight
advancements
accomplishments
in
mechanochemistry,
underscoring
its
potential
as
viable
eco-friendly
conventional
solution-based
methods
the
field
synthetic
chemistry.
Chemical Science,
Год журнала:
2022,
Номер
13(22), С. 6583 - 6591
Опубликована: Янв. 1, 2022
Low-valent
group
2
(E
=
Be
and
Mg)
stabilized
compounds
have
been
long
synthetically
pursued.
Here
we
discuss
the
electronic
structure
of
a
series
Lewis
base-stabilized
Mg
compounds.
Despite
accepted
zero(0)
oxidation
state
nature
elements
some
recent
experimentally
accomplished
species,
analysis
multireference
wavefunctions
provides
compelling
evidence
for
strong
diradical
character
with
an
+2.
Thus,
elaborate
on
distinction
between
description
as
donor-acceptor
interaction
L(0)
⇆
E(0)
⇄
internally
oxidized
situation,
better
interpreted
L(-1)
→
E(+2)
←
species.
The
examples
rely
strengthened
bonds
by
increasing
π-acidity
ligand;
avoiding
this
could
lead
to
unprecedented
low-oxidation
state.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(3)
Опубликована: Ноя. 25, 2022
Complex
[(DIPeP
BDI)Ca]2
(C6
H6
),
with
a
C6
H62-
dianion
bridging
two
Ca2+
ions,
reacts
benzene
to
yield
(biphenyl)
biphenyl2-
(DIPeP
BDI=HC[C(Me)N-DIPeP]2
;
DIPeP=2,6-CH(Et)2
-phenyl).
The
biphenyl
complex
was
also
prepared
by
reacting
)
or
reduction
of
BDI)CaI]2
KC8
in
presence
biphenyl.
Benzene-benzene
coupling
observed
when
the
deep
purple
product
ball-milling
[(DIPP
BDI)CaI(THF)]2
K/KI
extracted
(DIPP=2,6-CH(Me)2
-phenyl)
giving
crystalline
BDI)Ca(THF)]2
(52
%
yield).
Reduction
BDI)SrI]2
gave
highly
labile
BDI)Sr]2
as
black
powder
(61
yield)
which
rapidly
and
selectively
(biphenyl).
DFT
calculations
show
that
most
likely
route
for
formation
is
pathway
attacks
neutral
benzene.
This
facilitated
metal-benzene
coordination.
