Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(31), P. 5768 - 5773
Published: Aug. 3, 2023
A
photoinduced
charge
transfer
complex
(CTC)-enabled
photoreduction
of
carborane
phosphonium
salts
for
the
cage
carbon
(hetero)arylation
carboranes
was
developed.
It
offers
a
convenient
approach
introducing
wide
range
aryl
and
heteroaryl
groups,
such
as
pyrroles,
thiophenes,
indoles,
thianaphthenes,
benzofurans,
pyridines,
benzenes,
into
carboranes.
This
strategy
operational
simplicity,
mild
reaction
conditions,
broad
substrate
scope,
making
it
highly
advantageous.
EES Catalysis,
Journal Year:
2023,
Volume and Issue:
1(4), P. 333 - 352
Published: Jan. 1, 2023
This
article
reviews
organic
photocatalyst
hydrogen
evolution
reaction
(HER),
discussing
the
excitonic
behaviour
and
improvement
strategies.
It
also
covers
progress
in
photocatalysts,
assesses
HER
efficiency
stability.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(11), P. 7791 - 7802
Published: March 10, 2024
The
development
of
new
synthetic
methods
for
B–H
bond
activation
has
been
an
important
research
area
in
boron
cluster
chemistry,
which
may
provide
opportunities
to
broaden
the
application
scope
clusters.
Herein,
we
present
a
reaction
strategy
direct
site-selective
functionalization
nido-carboranes
initiated
by
photoinduced
cage
via
noncovalent
cage···π
interaction.
As
result,
nido-carborane
radical
is
generated
through
single
electron
transfer
from
3D
2D
photocatalyst
upon
irradiation
with
green
light.
resulting
transient
could
be
directly
probed
advanced
time-resolved
EPR
technique.
In
air,
subsequent
transformations
active
have
led
efficient
and
selective
B–N,
B–S,
B–Se
couplings
presence
N-heterocycles,
imines,
thioethers,
thioamides,
selenium
ethers.
This
protocol
also
facilitates
both
late-stage
modification
drugs
synthesis
nido-carborane-based
drug
candidates
neutron
capture
therapy
(BNCT).
Molecules,
Journal Year:
2025,
Volume and Issue:
30(4), P. 879 - 879
Published: Feb. 14, 2025
A
novel
fluoride
ion
fluorescent
probe
is
designed
by
introducing
the
strong
electron-withdrawing
triazine
groups
into
triarylboron/acridine
conjugation
system.
The
A-D-A'
molecular
configuration
endows
this
molecule
with
multiple
charge-transfer
channels;
upon
reaction
F-,
act
as
primary
acceptors
within
molecule,
facilitating
charge
transfer
between
acridine
units
and
groups.
During
detection,
changes
in
triarylboron
moiety
lead
to
a
significant
bathochromic-shift
fluorescence
emission
from
green
yellow.
Theoretical
calculations
attribute
phenomenon
reduction
S1
state
energy
level
fluorination,
resulting
pronounced
visible
color
change
chromogenic
response
during
detection.
Based
on
intensity
varying
degrees
of
F-
coordination,
detection
limit
low
10-7
M
was
determined
for
TB-1DMAc-2TRZ,
demonstrating
high
sensitivity
probe.
Beilstein Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
21, P. 412 - 420
Published: Feb. 21, 2025
A
new
series
of
o
-carborane-fused
pyrazoles
has
been
recently
successfully
synthesized.
This
fusion
was
expected
to
create
a
hybrid
3D/2D
aromatic
system,
combining
the
3D
aromaticity
-carborane
with
2D
pyrazole.
However,
while
boron
cage
retains
its
character,
pyrazole’s
is
lost.
As
result,
rather
than
forming
pyrazoles,
synthesis
yielded
pyrazolines,
which
are
non-aromatic.
The
limited
overlap
between
π
molecular
orbitals
(MOs)
planar
heterocycle
and
n
+
1
MOs
carborane
prevents
significant
electronic
delocalization
two
fused
components.
contrasts
pyrazole
benzene
form
indazole,
where
both
rings
maintain
their
aromaticity.
Our
findings
demonstrate
that
peripheral
σ-aromaticity
π-aromaticity
orthogonal,
making
true
system
unachievable.
highly
aromatic,
generating
negative
NICS
values
(−25
−30
ppm).
We
have
observed
these
high
extend
rings,
leading
incorrect
estimations
Therefore,
relying
solely
on
can
be
misleading,
other
computational
indicators,
along
experimental
or
structural
data,
should
used
accurately
assess
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(31)
Published: April 29, 2023
Visible-light-induced
photoreaction
of
carboranes
is
an
effective
approach
to
prepare
carborane-containing
compounds.
While
several
methods
involving
boron-centered
carboranyl
radicals
have
been
established,
those
for
carbon-centered
are
underdeveloped,
except
the
UV-light-promoted
photohomolysis.
Herein,
we
describe
a
simple
but
access
by
photoreduction
carborane
phosphonium
salts
under
blue
light
irradiation
without
using
transition
metals
and
photocatalysts.
The
utility
method
was
demonstrated
successfully
preparing
range
carborane-oxindole-pharmaceutical
hybrids
radical
cascade
reactions.
Computational
experimental
studies
suggest
that
generated
single-electron
transfer
photoactive
charge-transfer
complexes
between
additive
potassium
acetate.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(23)
Published: April 3, 2024
Abstract
Hypergolic
propellants
rely
on
fuel
and
oxidizer
that
spontaneously
ignite
upon
contact,
which
fulfill
a
wide
variety
of
mission
roles
in
launch
vehicles
spacecraft.
Energy‐rich
carboranes
are
promising
hypergolic
fuels,
but
triggering
their
energy
release
is
quite
difficult
because
ultrastable
aromatic
cage
structure.
To
steer
the
development
carborane‐based
high‐performance
material,
carboranylthiolated
compounds
integrated
with
atomically
precise
copper
clusters
presented,
yielding
two
distinct
isomers,
Cu
14B‐S
14C‐S
,
both
possessing
similar
ligands
core
structures.
With
migration
thiolate
groups
from
carbon
atoms
to
boron
atoms,
ignition
delay
(ID)
time
shortened
6870
3
ms
when
contacted
environmentally
benign
high‐test
peroxide
(HTP,
H
2
O
concentration
90%).
The
extraordinarily
short
ID
ranking
among
best
HTP‐active
materials.
experimental
theoretical
findings
reveal
benefitting
groups,
characterized
by
an
electron‐rich
metal
kernel,
displays
enhanced
reducibility
superior
charge
transfer
efficiency.
This
results
exceptional
activation
rates
HTP,
consequently
inducing
carborane
combustion
simultaneous
energy.
fundamental
investigation
shed
light
advanced
green
propulsion
systems.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(26), P. 17956 - 17963
Published: June 8, 2024
Conjugation
between
three-dimensional
(3D)
carboranes
and
the
attached
substituents
is
commonly
believed
to
be
very
weak.
In
this
paper,
we
report
that
reducing
1,12-bis(BMes2)-p-carborane
(B2pCab)
with
one
electron
gives
a
radical
anion
centrosymmetric
semiquinoidal
structure.
This
shows
extensive
delocalization
two
boron
centers
over
p-carborane
bridge
due
overlap
of
carborane
lowest
unoccupied
molecular
orbital
(LUMO)
BMes2
LUMO.
Unlike
dianions
other
C2B10H12
carboranes,
which
rearrange
nido-form,
two-electron
reduction
B2pCab
leads
rearrangement
into
basket-shaped
intermediate.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(61)
Published: Aug. 29, 2024
Abstract
The
possible
aromatic
conjugation
between
3D
and
2D
units
is
in
the
focus
since
synthesis
of
benzocarborane.
It
has
been
showed
that
icosahedral
1,2‐dicarba‐
closo
‐dodecaborane
systems
fused
with
rings
a
global
3D/2D
aromaticity
does
not
exist.
Despite
this
fact
during
last
years
several
studies
proposed
interactions
moieties.
Herein,
while
tuning
size
effective
charge
(car)borane
systems,
we
demonstrate
character
can
be
excluded
any
investigated
cases,
detectable
conjugative
properties
explained
effect
well‐known
negative
hyperconjugation.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 3, 2025
Selective
functionalization
of
o-carboranes
has
received
tremendous
attention,
specifically
in
the
regioselective
modification
ten
chemically
similar
BH
vertices
within
o-carborane
cage.
We
disclose
herein
a
strategy
for
palladium-catalyzed
esterification
B(3)-H
bond
using
tungsten
hexacarbonyl
as
carbon
monoxide
source.
The
corresponding
functionalized
were
prepared
moderate
to
very
good
yields
with
excellent
regioselectivity.
Dalton Transactions,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
Pd-catalyzed
intramolecular
annulation
of
1-acylamino-
o
-carboranes
was
developed
for
the
synthesis
-carboranoxazoles,
where
chlorobenzene
acted
as
an
external
oxidant.
