Chemical Communications,
Год журнала:
2023,
Номер
59(67), С. 10117 - 10120
Опубликована: Янв. 1, 2023
A
systematic
study
on
the
reactivity
of
cyclo-P4
complexes
[CpRTa(CO)2(η4-P4)]
towards
pnictogenium
cations
results
in
formation
functionalised
interpnictogen
cations.
Phosphenium
ions
insert
into
one
P-P
bonds
to
give
ring-expanded
cyclo-P5R2
products.
In
contrast,
an
arsenium-functionalised
P4AsCy2
ligand
displays
interesting
borderline
case
between
ring
expansion
and
coordination,
while
stibenium
afford
addition
Tuning
steric
electronic
properties
ion
shows
a
drastic
influence
reaction
outcome.
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.
Science,
Год журнала:
2024,
Номер
385(6706), С. 305 - 311
Опубликована: Июль 18, 2024
Precise
modification
of
a
chemical
site
in
molecule
at
the
single-atom
level
is
one
most
elegant
yet
difficult
transformations
chemistry.
A
reagent
specifically
designed
for
chemoselective
introduction
monoatomic
carbon
particularly
formidable
challenge.
Here,
we
report
straightforward,
azide-free
synthesis
crystalline
and
isolable
diazophosphorus
ylide,
Ph
JACS Au,
Год журнала:
2024,
Номер
4(5), С. 1709 - 1722
Опубликована: Апрель 15, 2024
How
different
is
carbon
compared
to
other
elements
in
the
periodic
table?
Can
compounds
be
regarded
as
coordination
complexes
with
central
element
undergoing
a
facile
exchange
of
its
ligands?
Although
clearly
plays
special
role
among
table,
recent
studies
have
drawn
parallels
between
bonding
situation
and
reactivity
transition
metal
complexes.
This
Perspective
summarizes
reports
about
ylidic
zwitterionic
that
were
shown
exhibit
ambiguous
situations
can
interpreted
donor–acceptor
interactions
similar
bond
neutral
ligand.
Based
on
this
conception,
ligand
reactions
prototypical
realized
at
atoms,
enabling
new
synthetic
strategies
for
synthesis
reactive
species
building
blocks.
In
particular,
N2,
CO,
phosphine
ligands
led
development
mild
method
accessing
reagents
unusual
properties,
such
vinylidene
ketenes
or
stable
ketenyl
anions,
open
up
diverse
but
still
poorly
explored
follow-up
chemistry.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(35)
Опубликована: Апрель 25, 2023
Over
decades
diazoalkenes
(R2
C=C=N2
)
were
postulated
as
reactive
intermediates
in
organic
chemistry
even
though
their
direct
spectroscopic
detection
proved
very
challenging.
In
the
1970/80ies
several
groups
probed
existence
mainly
indirectly
by
trapping
experiments
or
directly
matrix-isolation
studies.
2021,
our
group
and
Severin
reported
independently
synthesis
characterization
of
first
room-temperature
stable
diazoalkenes,
which
initiated
a
rapidly
expanding
research
field.
Up
to
now
four
different
classes
N-heterocyclic
substituted
have
been
reported.
Their
properties
unique
reactivity,
such
N2
/CO
exchange
utilization
vinylidene
precursors
transition
metal
are
presented.
This
review
summarizes
early
discoveries
from
initial
postulation
transient,
elusive
species
up
recent
findings
derivatives.
Organometallics,
Год журнала:
2024,
Номер
43(4), С. 585 - 593
Опубликована: Фев. 15, 2024
Ketenyl
anions
are
versatile
intermediates
in
synthetic
chemistry
and
have
recently
become
accessible
as
isolable
reagents
from
metalated
ylides
by
exchange
of
the
phosphine
with
CO.
Herein,
we
report
on
a
systematic
study
substituent
effects
structure
bonding
situation
ketenyl
anions.
A
series
phosphinoyl-substituted
{[R
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(20)
Опубликована: Март 12, 2024
Abstract
Cumulenes
and
heterocumulenes
with
three
or
more
cumulative
multiple
bonds
are
usually
reactive
species
that
serve
as
valuable
building
blocks
for
complex
molecules
but
tend
to
isomerize
cyclize
therefore
difficult
isolate.
Using
a
mild
ligand
exchange
reaction
at
the
carbon
in
α‐metalated
ylides,
we
have
now
succeeded
synthesis
gram‐scale
isolation
of
elusive
cyanoketenyl
anion
[NC
3
O]
−
.
Despite
its
assumed
cumulene‐like
structure
delocalization
negative
charge
across
whole
5‐atom
molecule,
it
features
bent
geometry
nucleophilic
central
atom.
Computational
studies
reveal
an
ambiguous
bonding
situation
anion,
which
can
be
illustrated
only
by
combination
different
resonance
structures.
Nonetheless,
remarkable
stability,
thus
allowing
storage
potassium‐crown
ether
salt
application
highly
functional
synthetic
block.
The
readily
reacts
series
small
form
organic
compounds,
including
industrially
compounds
such
cyanoacetate.
This
work
demonstrated
generated
novel
methods
open
up
atom‐economic
pathways
from
abundant
molecules.
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.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 11, 2025
The
Wolff
rearrangement
(WR)
is
widely
used
for
the
synthesis
of
ketenes
from
diazoketones
and
-esters.
Stepwise
WR
reactions
are
proposed
to
proceed
through
transient
carbonylcarbene
(R–C–C(O)–R′)
intermediates,
which
so
far
have
evaded
structural
characterization.
Here,
a
metallocarbene
(PtII–C–C(O)–OEt)
reported
as
fleeting
intermediate
in
photoinitiated
fragmentation
diazoester
ligand.
Frozen
solution
crystal
matrix
isolation
experiments
enabled
spectroscopic,
magnetic,
crystallographic,
computational
characterization
this
highly
reactive
species.
All
methods
confirmed
singlet
ground
state
metallocarbene,
stabilized
by
π
interactions
with
carboxyl
substituent,
thus
complementing
spectroscopy
studies
classic
organic
reactions.
