Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 31, 2024
Abstract
A
1,4,2‐diazasilole
containing
a
low‐valent
silicon
atom
has
been
synthesized
employing
bulky
imino
N‐heterocyclic
carbene
ligand.
This
molecular
structure
is
characterized
by
mesoionic
C
2
N
Si
five‐membered
ring,
notable
for
its
delocalized
π
electrons,
intrinsic
charge‐separated
zwitterionic
properties,
and
distinctly
nucleophilic
center,
culminating
in
6π
aromaticity.
compound
manifests
either
silylene
or
silylone
characteristics
upon
coordination
with
transition
metals.
Demonstrating
extraordinary
versatility,
this
engages
diverse
reactions
such
as
iron
iridium,
oxidation
S
8
,
intramolecular
ring
saturation
under
the
influence
of
transfer
facilitated
Ph
Se
contraction
induced
Te
skeletal
rearrangement
triggered
Et
3
N•HCl.
These
culminate
formation
variety
unprecedented
silicon‐based
heterocycles,
which
are
typically
formidable
to
achieve
using
conventional
methods.
study
unveils
previously
unexplored
facets
1,4,2‐diazasilole,
positioning
it
promising
foundational
building
block
future
innovations
unique
compounds.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(8), С. 3896 - 3951
Опубликована: Янв. 1, 2024
This
review
provides
an
overview
of
main
group
carbene
analogues,
covering
recent
advancements,
synthesis
strategies,
and
the
diverse
reactivity
elements
in
groups
13–15
based
on
their
structural
characteristics.
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 22, 2025
ConspectusThe
advancement
of
synthetic
methodologies
is
fundamentally
driven
by
a
deeper
understanding
the
structure–reactivity
relationships
reactive
key
intermediates.
Carbyne
anions
are
compounds
featuring
monovalent
anionic
carbon
possessing
four
nonbonding
valence
electrons,
which
were
historically
confined
to
theoretical
constructs
or
observed
solely
within
environment
gas-phase
studies.
These
species
possess
potential
for
applications
across
diverse
domains
chemistry
and
ancillary
fields.
This
Account
details
our
focused
efforts
isolate
singlet
carbyne
explores
isolation
range
related
low-valent
species.
Our
achievements
include
synthesis
characterization,
under
normal
laboratory
conditions,
gold-substituted
free
carbenes,
copper
anion
complexes,
ketenyl
anions,
keteniminyl
stannyne.
have
been
accomplished
using
bulky
cyclic
phosphino
substituent,
effectively
stabilizes
these
species.Our
journey
commenced
with
phosphinocarbenes,
characterized
robust
carbon–gold
covalent
single
bond,
progressed
complexes
carbon–copper
ionic
bond.
was
realized
through
synergistic
combination
group
closed-shell
electron-rich
late
transition
metal.
The
robustness
bond
contrasts
markedly
susceptibility
imparts
behavior
characteristic
phosphinocarbyne
coordination
sphere
copper,
thereby
enabling
unique
transfer
reactions.
tri-active
ambiphilic
nature
in
enables
formation
three
chemical
bonds
at
center
one-pot
Subsequent
investigations
unveiled
ligand
exchange
reactions
site,
leading
generation
stable
crystalline
anions.
emerge
as
potent
synthons
capable
producing
array
derivatives.
In
addition,
we
isolated
phosphinostannyne,
rare
carbon–tin
multiple
two
adjacent
centers.
Collectively,
demonstrated
remarkable
propensity
engaging
spectrum
reactions,
underscoring
their
versatility
confirming
utility
synthesizing
uncharted,
main
species.The
insights
derived
from
research
contribute
broader
may
provide
platform
future
innovations
chemistry,
catalytic
processes,
novel
materials.
As
continue
explore
develop
this
area
study,
hope
that
might
follow
footsteps
potentially
finding
various
fields
future.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 29, 2024
Abstract
Phosphanorcaradienes
are
an
appealing
class
of
phosphorus
compounds
that
can
serve
as
synthons
transient
phosphinidenes.
However,
the
synthesis
such
species
is
a
formidable
task
owing
to
their
intrinsic
high
reactivity.
Herein
we
report
straightforward
synthesis,
characterization
and
reactivity
studies
phosphanorcaradiene,
in
which
one
benzene
rings
flanking
fluorenyl
substituents
intramolecularly
dearomatized
through
attachment
atom.
It
facilely
obtained
by
reduction
phosphorus(III)
dichloride
precursor
with
potassium
graphite.
Despite
being
thermally
robust,
it
acts
synthetic
equivalent
phosphinidene.
reacts
trimethylphosphine
isonitrile
yield
phosphanylidene-phosphorane
1-phospha-3-azaallene,
respectively.
When
treated
two
molar
equivalents
azide,
iminophosphane
bis(imino)phosphane
isolated,
Moreover,
capable
activating
ethylene
alkyne
afford
[1
+
2]
cycloaddition
products,
well
oxidative
cleavage
Si–H
N–H
bonds
secondary
phosphines.
All
reactions
proceed
smoothly
at
room
temperature
without
presence
transition
metals.
The
driving
force
for
these
most
likely
ring-constraint
three-membered
PC
2
ring
recovery
aromaticity
ring.
Chemical Communications,
Год журнала:
2024,
Номер
60(72), С. 9793 - 9796
Опубликована: Янв. 1, 2024
The
synthesis
of
a
(phosphino)(stannyl)carbene
is
documented.
combination
phosphino
and
stannyl
substituents
imparts
highly
ambiphilic
nature
to
this
carbene,
enabling
reactions
with
cyanide,
isocyanide,
carbon
monoxide.
This
leads
rare
stannylketenimines
stannylketene.
