International Journal of Molecular Sciences,
Journal Year:
2021,
Volume and Issue:
22(24), P. 13391 - 13391
Published: Dec. 13, 2021
In
the
present
work,
a
convenient
and
straightforward
approach
to
preparation
of
borylated
amidines
based
on
closo-dodecaborate
anion
[B12H11NCCH3NHR]−,
R=H,
Alk,
Ar
was
developed.
This
method
has
two
stages.
A
nitrile
derivative
general
form
[B12H11NCCH3]−
obtained,
using
modified
technique,
in
first
stage.
On
second
stage
resulting
molecular
system
interacted
with
primary
amines
target
amidine
products.
is
characterised
by
simple
chemical
apparatus,
mild
conditions
high
yields
final
The
mechanism
addition
amine
studied,
quantum-chemical
methods.
interaction
between
NH3
ammonia
chosen
as
an
example.
It
found
that
structure
transition
state
determines
stereo-selectivity
process.
study
biological
properties
sodium
salts
indicated
substances
had
low
toxicity
could
accumulate
cancer
cells
significant
amounts.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(23), P. 8800 - 8816
Published: Oct. 18, 2019
Abstract
Boron's
unique
position
in
the
Periodic
Table,
that
is,
at
apex
of
line
separating
metals
and
nonmetals,
makes
it
highly
versatile
chemical
reactions
applications.
Contemporary
demand
for
renewable
clean
energy
as
well
energy‐efficient
products
has
seen
boron
playing
key
roles
energy‐related
research,
such
1)
activating
synthesizing
energy‐rich
small
molecules,
2)
storing
electrical
energy,
3)
converting
into
light.
These
applications
are
fundamentally
associated
with
boron's
characteristics,
its
electron‐deficiency
availability
an
unoccupied
p
orbital,
which
allow
formation
a
myriad
compounds
wide
range
physical
properties.
For
example,
ability
to
achieve
full
octet
electrons
four
covalent
bonds
negative
charge
led
synthesis
variety
borate
anions
high
electrochemical
stability—in
particular,
weakly
coordinating
anions.
This
Review
summarizes
recent
advances
study
processes
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(10), P. 5889 - 5985
Published: April 16, 2021
The
history
of
silyl
cations
has
all
the
makings
a
drama
but
with
happy
ending.
Being
considered
reactive
intermediates
impossible
to
isolate
in
condensed
phase
for
decades,
their
actual
characterization
solution
and
later
solid
state
did
only
fuel
discussion
about
existence
initially
created
lot
controversy.
This
perception
completely
changed
today,
donor-stabilized
congeners
are
now
widely
accepted
compounds
promising
use
synthetic
chemistry.
review
provides
comprehensive
summary
fundamental
facts
principles
chemistry
cations,
including
reliable
ways
preparation
as
well
physical
chemical
properties.
striking
features
enormous
electrophilicity
such
reactivity
super
Lewis
acids
fluorophilicity.
Known
applications
rely
on
reactants,
stoichiometric
reagents,
promoters
where
reaction
success
is
based
steady
regeneration
over
course
reaction.
Silyl
can
even
be
discrete
catalysts,
thereby
opening
next
chapter
way
into
toolbox
methodology.
Accounts of Chemical Research,
Journal Year:
2021,
Volume and Issue:
54(21), P. 4065 - 4079
Published: Oct. 24, 2021
ConspectusCarboranes
are
a
class
of
polyhedral
carbon-boron
molecular
clusters
featuring
three-dimensional
aromaticity,
which
often
considered
as
3D
analogues
benzene.
Their
unique
structural
and
electronic
properties
make
them
invaluable
building
blocks
for
applications
ranging
from
functional
materials
to
versatile
ligands
pharmaceuticals.
Thus,
selective
functionalization
carboranes
has
received
tremendous
research
interest.
In
earlier
days,
the
vast
majority
works
in
this
area
were
focused
on
cage
carbon
via
facile
deprotonation
CH,
followed
by
reaction
with
electrophiles.
On
contrary,
B-H
activation
is
very
challenging
since
10
bonds
o-carborane
similar,
how
achieve
desired
transformation
at
specific
boron
vertex
long-standing
issue.As
more
electronegative
than
boron,
property
results
different
charges
cage,
follow
order
B(3,6)-H
≪
B(4,5,7,11)-H
<
B(8,10)-H
B(9,12)-H.
We
thought
that
difference
may
trigger
favorite
interaction
proper
transition
metal
complex
bond
carborane,
could
be
utilized
solve
selectivity
issue.
Accordingly,
our
strategy
described
follows:
(1)
electron-rich
catalysts
good
most
electron-deficient
(connected
both
C-H
vertices);
(2)
relatively
B(8,9,10,12)-H
(with
no
bonding
either
(3)
directing-group-assisted
catalysis
appropriate
only
one
vertex),
whose
lie
middle
range
bonds.
This
been
successfully
applied
laboratory
other
groups
development
series
synthetic
routes
catalytic
carborane
resulting
synthesis
large
number
cage-boron-functionalized
derivatives
regioselective
fashion.
Subsequently,
significant
progress
emerging
made.In
2013
we
reported
tetrafluorination
o-carboranes
using
an
Pd(II)
salt,
[Pd(MeCN)4][BF4],
catalyst.
2014
disclosed
first
example
carboxy-directed
alkenylation
B(4)
promoted
Ir(III)
2017
presented
Ir(I)-catalyzed
diborylation
also
uncovered
Pd-catalyzed
asymmetric
chiral-at-cage
2018.
These
proof-of-principle
studies
have
greatly
stimulated
activities
enabled
catalysts.
so
far
developed
toolbox
methods
B-olefination,
-arylation,
-alkenylation,
-alkynylation,
-oxygenation,
-sulfenylation,
-borylation,
-halogenation,
-amination.
recently
expanded
base
catalysis.
As
field
progresses,
expect
will
invented,
detailed
Account
promote
these
efforts.
ACS Central Science,
Journal Year:
2024,
Volume and Issue:
10(2), P. 264 - 271
Published: Jan. 12, 2024
To
realize
an
energy
storage
transition
beyond
Li-ion
competitive
technologies,
earth-abundant
elements,
such
as
Mg,
are
needed.
Carborane
anions
particularly
well-suited
to
realizing
magnesium-ion
batteries
(MIBs),
their
inert
and
weakly
coordinating
properties
beget
excellent
electrolyte
performance.
However,
utilizing
these
materials
in
actual
electrochemical
cells
has
been
hampered
by
the
reliance
on
Mg2+
salts
of
commercially
available
[HCB11H11]−
anion,
which
is
not
soluble
more
binding
solvents
apart
from
higher
glymes.
Herein,
we
demonstrate
it
possible
iteratively
engineer
anion
surface
synthetically
address
previous
solubility
issues
yield
a
highly
conductive
(up
7.33
mS
cm–1)
electrochemically
stable
+4.2
V
vs
Mg2+/0)
magnesium
that
surpasses
state
art.
This
novel
non-nucleophilic
exhibits
dissociative
behavior
regardless
concentration
tolerant
prolonged
periods
cycling
symmetric
at
high
current
densities
2.0
mA
cm–2,
400
h).
The
hydrocarbon
functionalized
carborane
presented
here
demonstrates
>96%
Coulombic
efficiency
when
paired
with
Mo6S8
cathode.
approach
realizes
needed
candidate
discover
next-generation
cathode
can
enable
design
practical
viable
Mg
batteries.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 14, 2025
Carboranyl
amines
are
distinct
from
typical
organic
amines.
Due
to
the
electronic
influence
of
carborane
cage,
they
have
low
nucleophilicity
and
reluctant
alkylate.
Moreover,
asymmetric
synthesis
chiral
carboranes
is
still
in
its
infancy.
Herein
we
achieved
first
catalytic
N-alkylation
o-carboranyl
amine,
providing
general
access
diverse
secondary
with
high
efficiency
enantioselectivity
under
mild
conditions.
For
time,
organocatalysis
was
introduced
chemistry.
Key
success
use
situ
generated
(naphtho-)quinone
methides
as
alkylating
reagents
suitable
acid
catalysts.
This
protocol
also
applicable
S-alkylation
1-SH-o-C2B10H11.
Control
experiments
kinetic
studies
provided
important
insights
into
reaction
mechanism,
which
likely
involves
rate-determining
generation
quinone
methide
followed
by
fast
enantio-determining
nucleophilic
addition.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(20), P. 11822 - 11840
Published: Sept. 14, 2020
The
field
of
Surface
Organometallic
Chemistry
(SOMC)
aims
to
blend
the
positive
attributes
homogeneous
and
heterogeneous
catalysis.
Significant
insight
into
systems
has
been
gained
over
years
through
synthesis,
characterization,
application
well-defined
surface
organometallic
catalysts,
predominantly
supported
on
silica
alumina.
Considerable
research
efforts
have
focused
methods
synthesis
characterization
these
systems.
Homogeneous
catalysis
thrived
its
ability
electronically
sterically
tune
ligands
yield
desired
reactivity
selectivity.
Efforts
in
SOMC,
however,
only
recently
turned
harnessing
stereoelectronic
diversity
potential
inorganic
support
materials
beyond
alumina
order
exert
similar
control
active
site.
material
is
intrinsically
linked
electronic
structure
same
way
that
catalyst
catalysts
by
changing
great
value,
it
anticipated
this
will
represent
an
area
significant
growth
field.
In
Perspective,
use
future
nontraditional
supports,
such
as
sulfated
metal
oxides,
modified
silicas,
redox
supports
are
discussed.
