Chemistry of three-dimensional icosahedral boron clusters anions: closo-dodecaborate (2-) [B12H12]2- and carba-closo-dodecaborate(-) [CB11H12]-
Lingyao Wang,
No information about this author
Yunjia Jiang,
No information about this author
Simon Duttwyler
No information about this author
et al.
Coordination Chemistry Reviews,
Journal Year:
2024,
Volume and Issue:
516, P. 215974 - 215974
Published: June 8, 2024
Language: Английский
Borenium Ylide-Mediated 12-B Arylation of Carborane Anions
Y Kitazawa,
No information about this author
Toshiki Inoue,
No information about this author
Yuta Koike
No information about this author
et al.
JACS Au,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 24, 2025
Developing
novel
approaches
for
B-vertex
modification
is
significant
in
the
chemistry
of
icosahedral
boron
clusters.
Here,
we
report
a
protocol
transformation
air-stable
12-aryliodonium
carborane
anions,
which
are
readily
accessible
on
gram
scale
from
corresponding
(diacetoxyiodo)arenes
(ArI(OAc)2)
and
anion,
to
12-aryl-carborane
anions.
Mechanistic
studies
support
idea
that
12-B
arylation
proceeds
via
intramolecular
reductive
C-B
bond
formation
12-borenium
ylide,
followed
by
rearomatization.
The
reaction
under
mild
conditions
air
suitable
one-pot
synthesis
without
need
purification
B-B
coupling
at
vertex
affords
dumbbell-type
anion
dimers.
This
offers
an
alternative
approach
B-C
closo
borates,
complementing
conventional
cross-coupling
approaches.
Language: Английский
Noncatalyzed Intramolecular B–N and B–O Cross-Coupling of “Inert” Carboranes Lead to the Formation of an Unusual Oxoborane, via Reversible Cluster C–B Bond Scission
Sergio Lovera,
No information about this author
Aaron Gregory,
No information about this author
Katherine Espinoza Morelos
No information about this author
et al.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 13, 2025
Polyhalogenated
closo-12-vertex
carborane
anions
are
thought
to
be
inert
species
incapable
of
participating
in
direct
B-X
substitution
reactions.
Here,
we
show
that
this
is
not
true
and
such
can
easily
coaxed
into
intramolecular
cross-coupling
cyclizations
without
the
need
for
a
catalyst.
When
cage
C-tethered
O
N-heteroallylic
generated,
variety
cyclized
products
formed
high
yield
under
mild
conditions.
Additionally,
even
neutral
nucleophiles,
as
pyridine
moiety,
undergo
facile
chemistry
these
reactions
dependent
on
countercation.
Serendipitously,
also
found
when
attempted
with
acetamide
derivatives,
an
unprecedented
cluster
C-B
bond
scission
reaction
occurs,
producing
oxoborane
stabilized
by
multicentered
bonding.
Amazingly
molecule
protonated,
leading
reformation
reorganization,
process
reversible.
Language: Английский
Synthesis of {CB11} Monocarborane Sulfonamides by B2‐Selective Rhodium‐Catalyzed B−H Activation
Zehua Ye,
No information about this author
Jizeng Sun,
No information about this author
Yujie Jin
No information about this author
et al.
Helvetica Chimica Acta,
Journal Year:
2023,
Volume and Issue:
106(11)
Published: Sept. 28, 2023
Abstract
The
synthesis
of
monocarborane
sulfonamides
is
reported.
methodology
relies
on
coupling
the
anionic
{CB
11
}
boron
cluster
to
sulfonyl
azides.
Under
rhodium
catalysis
and
with
assistance
a
pyridine
or
pyrimidine
directing
group
at
C1
position,
undergoes
B−H
activation.
Conditions
have
been
identified
that
lead
B2‐selective
mono‐sulfonamidation
concomitant
loss
N
2
.
protocol
requires
no
additional
ligand,
oxidant
base
enables
B−N
bond
formation
various
azide
inputs.
new
products
possess
structure
[1‐(heteroaryl)‐2‐(NHSO
Ar)−CB
H
10
]
−
fully
characterized
by
NMR
spectroscopy
mass
spectrometry.
In
addition,
three
solid
state
structures
confirm
particular
B2
substitution
pattern.
Furthermore,
stoichiometric
reaction
pyridinyl
precursor
Rh(III)
affords
cyclometalated
complex
direct
B−Rh
has
also
X‐ray
crystallography.
Language: Английский