The
Lewis
acidity
of
primary,
secondary,
and
tertiary
boranes
with
phenyl,
pentafluorophenyl,
all
three
isomers
icosahedral
carboranes
(ortho,
meta,
para)
were
investigated
by
computing
their
fluoride,
hydride,
ammonia
affinities
as
well
global
electrophilicity
indices
LUMO
energies.
From
these
calculations,
the
substituent
effects
on
follow
trend
ortho-carborane
>
meta-carborane
para-carborane
C6F5
C6H5.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(13), P. 7331 - 7342
Published: March 24, 2023
Herein,
we
present
a
chemically
robust
and
efficient
synthesis
route
for
B(9)-OH-o-carboranes
by
the
oxidation
of
o-carboranes
with
commercially
available
68%
HNO3
under
assistance
trifluoromethanesulfonic
acid
(HOTf)
hexafluoroisopropanol
(HFIP).
The
reaction
is
highly
wide
scope
carboranes,
selectivity
B(9)/B(8)
up
to
98:2.
success
this
transformation
relies
on
strong
electrophilicity
oxidizability
HNO3,
promoted
through
hydrogen
bonds
Brønsted
HOTf
solvent
HFIP.
Mechanism
studies
reveal
that
o-carborane
involves
an
initial
electrophilic
attack
atom
at
most
electronegative
B(9)
o-carborane.
In
transformation,
B-H
bond
nucleophilic
site,
which
different
from
substitution
reaction,
where
boron
site.
Therefore,
oxidation-reduction
mild
conditions
in
N(V)
→
N(III)
H(-I)
H(I).
derivatization
9-OH-o-carborane
was
further
examined,
carboranyl
group
successfully
introduced
amino
acid,
polyethylene
glycol,
biotin,
deoxyuridine,
saccharide.
Undoubtedly,
approach
provides
selective
way
rapid
incorporation
carborane
moieties
into
small
molecules
application
neutron
capture
therapy,
requires
targeted
delivery
boron-rich
groups.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(13), P. 4839 - 4845
Published: Jan. 1, 2024
A
range
of
novel
o
-carboranyl
substituted
boron
compounds
have
been
synthesized
through
reactions
between
an
-carborane-fused
aminoborirane
and
various
organic
azides.
The
reaction
selectivity
mechanisms
were
studied
using
DFT
calculations.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
30(1)
Published: Sept. 27, 2023
New
developments
in
the
field
of
Lewis
acidity
are
highlighted,
with
focus
novel
acids
and
superacids
group
2,
13,
14,
15
elements.
Several
important
basics,
illustrated
by
modern
examples
(classification
Donor-Acceptor
(DA)
complexes,
amphoteric
nature
any
compound
terms
DA
interactions,
reorganization
energies
main
role
frontier
orbitals)
presented
discussed.
It
is
emphasized
that
phenomena
general
play
vital
different
areas
chemistry:
from
weak
"atomophilic"
interactions
to
complexes
superacids.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(42)
Published: April 26, 2023
In
this
contribution,
we
reported
the
three-dimensional
(3D)
analogues
of
N-heterocyclic
carbene
(NHC)-stabilized
9-borafluorenium
and
9-borafluorene
radical.
The
radical
was
fully
characterized
by
cyclic
voltammetry
(CV),
UV-Vis
absorption
spectroscopy,
electron
paramagnetic
resonance
(EPR)
single-crystal
X-ray
diffraction
analyses.
distinct
boron-centered
character
corroborated
DFT
calculations
EPR
analysis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(34)
Published: June 20, 2023
The
Lewis
superacid,
bis(1-methyl-ortho-carboranyl)borane,
is
rapidly
accessed
in
two
steps.
It
a
very
effective
hydroboration
reagent
capable
of
B-H
addition
to
alkenes,
alkynes,
and
cyclopropanes.
To
date,
this
the
first
identified
superacidic
secondary
borane
most
reactive
neutral
reagent.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 20, 2025
Herein,
we
report
that
ArLi,
formed
in
situ
through
the
Li/Br
exchange
between
aryl
bromide
and
n-butyllithium,
can
undergo
rapid
intramolecular
Li/H(Ccage–H)
to
functionalize
o-carboranes.
Based
on
this
observation,
a
dual
C–H
lithiation
reaction
of
2-
or
3-o-carboryl
benzothiophenes
was
developed,
series
o-carborane-fused
phospholes
were
synthesized
by
dilithio
compounds
with
chlorophosphine.
This
is
simple
high
chemical
selectivity
medium
yields.
It
also
be
applied
furan
derivative.
Stability
studies
demonstrated
these
phosphole
derivatives
are
stable
both
trivalent
coordination
states
for
phosphorus.
In
contrast,
their
oxides
sensitive
moisture
air
susceptible
attack
nucleophiles,
leading
breakage
Ccage-P
bond.
Computational
results
indicate
newly
generated
rings
have
weak
aromaticity.
Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(33), P. 13495 - 13504
Published: Aug. 10, 2023
The
Lewis
acidity
of
primary,
secondary,
and
tertiary
boranes
with
phenyl,
pentafluorophenyl,
all
three
isomers
the
C-substituted
icosahedral
carboranes
(ortho,
meta,
para)
was
investigated
by
computing
their
fluoride,
hydride,
ammonia
affinities
as
well
global
electrophilicity
indices
LUMO
energies.
From
these
calculations,
it
determined
that
substituent
effects
on
follow
trend
ortho-carborane
>
meta-carborane
para-carborane
C6F5
C6H5.
Dalton Transactions,
Journal Year:
2024,
Volume and Issue:
53(10), P. 4444 - 4450
Published: Jan. 1, 2024
Biscarborane
dithiol
and
its
bis(methyl)thioether
feature
exceedingly
long
intracluster
C–C
bond
lengths,
consistent
with
the
increased
π-backdonation
of
sulfur
atom
lone
pairs
into
electron-accepting
boron
cluster.