Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
64(1), P. 268 - 274
Published: Dec. 26, 2024
Improved
methods
for
the
synthesis
of
B10H14
and
a
series
N-heterocycle-coordinated
B9H13
complexes
(N-Het·B9H13)
have
been
developed
with
readily
obtained
KB11H14
as
starting
material.
Oxidation
could
provide
in
over
90%
yield.
Then,
N-Het·B9H13
were
prepared
from
as-synthesized
through
situ
multistep
reactions
by
reacting
NaH,
N-heterocycles,
dilute
hydrochloric
acid.
Among
these
complexes,
4-(triphenylvinyl)pyridine-coordinated
(1k)
exhibits
significant
aggregation-induced
emission
(AIE)
effect
THF/H2O
mixed
solution,
8-aminoisoquinoline-coordinated
(2p)
positive
solvatochromism
phenomenon.
These
improved
new
approaches
to
synthesizing
potential
applications
luminescent
materials.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 13, 2024
The
innovation
of
synthetic
strategies
for
selective
B-H
functionalization
is
a
pivotal
objective
in
the
realm
boron
cluster
chemistry.
However,
precise,
efficient,
and
rapid
bond
carboranes
that
distant
from
existing
functional
groups
remains
intractable
owing
to
limited
approaches
site-selective
control
established
methods.
Herein,
we
report
dative
bonding
activation
strategy
nonclassical
remote
site
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 17, 2025
A
palladium-catalyzed
Heck-type
cross-coupling
reaction
of
carboranes
with
alkenes
in
1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP)
was
realized.
This
shows
good
B(9)
selectivity
for
m-carboranes
and
is
also
suitable
o-
p-carborane.
Meanwhile,
a
series
mono-,
di-,
trisubstituted
were
compatible
substrates
to
afford
the
alkenylated
products
16–89%
yields.
The
1,2-bis(carboranyl)ethylene
first
synthesized
by
vinyltrimethylsilane
m-carborane.
Further
transformations
C═C
bond
product
examined
hydroboration
oxidation,
hydroboration,
bromination
generate
corresponding
B(9)-functionalized
m-carboranes.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 1, 2025
The
selective
functionalization
of
inert
B–H
bonds
in
carborane
clusters
has
been
a
formidable
challenge.
Recent
advances
have
witnessed
such
reactions
through
photoredox
methods
utilizing
ultraviolet
or
visible
light
irradiation.
However,
high-energy
sources
often
suffer
from
poor
energy
efficiency,
limited
substrate
scope,
undesired
side
reactions,
and
low
scalability.
Here,
we
present
the
first
successful
bond
under
low-energy
near-infrared
(NIR)
using
carborane-based
electron
donor–acceptor
complex.
Both
photophysical
investigations
theoretical
modeling
reveal
facile
single-electron
transfer
cage
to
electron-deficient
photocatalyst,
generating
radical
NIR
follow-up
pathway
enables
direct
coupling
carboranes
with
amino
acids
oligopeptides,
yielding
diverse
array
carborane-functionalized
oligopeptides.
Beyond
expanding
known
chemical
space
boron
cluster
derivatives,
further
demonstrate
that
imaging
targeting
capabilities
could
serve
as
promising
multifunctional
carriers
for
neutron
capture
therapy.
Thus,
via
not
only
provides
straightforward
practical
strategy
synthetic
chemistry
but
also
lays
foundation
development
next-generation
boron-containing
biomolecules
advanced
functional
materials.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
Despite
significant
progress
in
the
B-H
functionalization
of
carboranes,
development
cost-effective
catalytic
systems
devoid
noble
metals,
coupled
with
mechanistic
validation
regioselectivity
control,
remains
a
formidable
challenge.
Herein,
we
disclose
an
Ag
salt-free,
redox-neutral,
and
inexpensive
ruthenium(ii)-catalyzed
protocol
that
enables
exclusive
B(4)-H
acylmethylation
o-carboranes
through
novel
post-coordination
strategy.
By
exploiting
weakly
coordinating
carboxylic
acid
as
traceless
directing
group,
this
method
achieves
excellent
mono-site
selectivity
for
B-C(sp3)
bond
formation
using
diverse
sulfoxonium
ylides,
demonstrating
both
functional
group
tolerance
synthetic
scalability.
This
work
not
only
establishes
practical
platform
but
also
addresses
critical
questions
unresolved
prior
analogous
studies.
Through
deuterium
labeling,
situ
high-resolution
mass
spectrometry
(HRMS)
tracking,
single-crystal
X-ray
analysis
Ru
intermediates,
unequivocally
demonstrate
originates
from
unique
mode
Ru(ii).
The
catalyst
simultaneously
engages
enolizable
acylmethyl
moiety
mono-acylated
intermediate,
thereby
dictating
activation
trajectory.
Our
findings
establish
generalizable
regiocontrolled
carborane
while
defining
paradigms
transition
metal-mediated
chemistry.
Physical Chemistry Chemical Physics,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
The
tris(
ortho
-carboranyl)borane
(BoCb
3
)
structure
enables
further
understanding
of
building
blocks
in
three-fold
architectures
as
useful
nodes
for
envisaging
cluster-based
materials
retaining
three
spherical
aromatic
circuits.
Journal of Physics B Atomic Molecular and Optical Physics,
Journal Year:
2024,
Volume and Issue:
57(16), P. 165102 - 165102
Published: July 24, 2024
Abstract
Recently,
the
Au–B
covalent
bonds
in
gold
doped
boron
clusters
has
attracted
great
attention.
However,
there
are
fewer
theoretical
reports
on
exploration
their
ground
state
structures
and
stabilities,
especially
for
medium
sizes.
Here,
we
study
structural
evolution
electronic
properties
of
anionic
Au
with
sizes
n
from
10
to
20
using
unbiased
cluster
searches
combined
density
functional
theory
(DFT)
calculations.
The
results
reveal
that
quasi-planar
AuB
18
−
(
1
A,
C
)
shows
excellent
stability
a
large
vertical
separation
energy
(VDE)
4.25
eV.
good
consistency
between
computationally
simulated
photoelectron
spectra
experimental
strongly
supports
correctness
our
low-lying
structures.
Further
bonding
analyses
show
well-stabilized
aromatic
is
due
active
σ
interactions
atom
(6
s
orbitals)
B
units
(2
p
orbitals),
as
well
number
–bonds
moiety
π
-aromaticity.
These
findings
enriched
family
Au-B
alloy
metal-doped
boron-based
clusters,
which
provide
valuable
information
characterization
preparation
boron-rich
nanoclusters
future.
Dalton Transactions,
Journal Year:
2024,
Volume and Issue:
53(33), P. 13960 - 13967
Published: Jan. 1, 2024
The
formation
of
molecular-based
functional
materials
is
a
key
step
towards
the
development
technologies
at
nanoscale.
Recently,
it
has
been
shown
that
after
oxidation
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: April 17, 2024
A
method
was
developed
to
link
two
or
three
o-carborane
moieties
form
a
series
of
carboranyl
dithioester
bridging
ligands
via
in
situ
substitution
haloalkanes
by
tetraphenylphosphonium
carboranyldithiocarboxylates.
Based
on
these
ligands,
direct
B-H
activation
without
the
assistance
Ag(I)
and
alkali
successfully
achieved
with
half-sandwich
Ir(III)
substrate
[Cp*IrCl
