Zeitschrift für anorganische und allgemeine Chemie,
Год журнала:
2024,
Номер
650(21)
Опубликована: Июль 12, 2024
Abstract
The
diaminoferrocene
derivative
fc[NH(BMes
2
)]
(
1
H
;
fc=1,1’‐ferrocenylene,
Mes=mesityl)
was
prepared
from
fc(NH
)
and
Mes
BCl
used
for
the
preparation
of
N‐heterocyclic
tetrylenes
fc{[N(BMes
E}
E,
E=Ge,
Sn)
via
sodium
amide
fc[NNa(BMes
Na
),
which
obtained
NaN(SiMe
3
.
is
inert
towards
LiN(SiMe
or
n
BuLi.
Its
reaction
with
BuLi
in
presence
TMEDA
afforded
TMEDA‐coordinated
lithium
Li
(TMEDA)
Crystallisation
THF
furnished
adduct
(THF)
Me
SiCl
(SiMe
Attempts
to
obtain
thiourea
C=S}
C=S)
Cl
C=S
were
not
successful.
accessible
)Cl
,
transformed
fc[(NH)
C=S]
by
NEt
(4
equiv.),
followed
conversion
fc{[N(SiMe
(2
equiv.)
subsequent
BCl.
All
new
compounds
except
structurally
characterised
single‐crystal
X‐ray
diffraction.
N
‐boryl
substituents
E
compete
efficiently
II
atom
nitrogen
π‐donation,
causing
comparatively
long
−N
bonds
small
bond
angles.
contains
a
four‐membered
BNCS
ring
due
intramolecular
formation
involving
Lewis
basic
S
acidic
B
atom.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 12, 2025
The
ongoing
discovery
of
highly
reactive
ambiphilic
main-group
species
has
significantly
advanced
the
development
chemistry,
particularly
in
realms
small
molecule
activation
and
catalysis.
Theoretically,
compounds
featuring
smaller
HOMO–LUMO
gaps
gain
stronger
ambiphilicity
higher
reactivity.
In
this
work,
we
fundamentally
demonstrate
that
Me3Sb
holds
smallest
gap
among
trimethylpnictines,
indicating
its
outstanding
ambiphilicity.
Correspondingly,
superior
reactivity
toward
deoxygenation
electron-deficient
nitroarenes
been
unambiguously
revealed
through
control
experiments.
Furthermore,
unprecedented
SbIII/SbVO
cycling
between
trialkylstibines
their
oxides
established
for
catalytic
transformation
into
azoxyarenes/azoarenes.
This
study
opens
a
new
chapter
organoantimony
derivatives
fields
redox
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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 18, 2024
Abstract
The
suitability
of
electron‐rich
bis‐silylenes,
specifically
the
neutral
chelating
[Si
II
(Xant)Si
]
ligand
(Si
=PhC(N
t
Bu)
2
Si,
Xant=9,9‐dimethylxanthene)
and
anionic
(N
Acrid
)Si
)]
−
pincer
=2,7,9,9‐tetramethylacridane),
has
been
successfully
probed
to
stabilize
monovalent
bis‐silylene‐supported
aluminium
complexes
(aluminylenes).
At
first,
unprecedented
aluminium(III)
iodide
precursors
]AlI
+
I
1
)]AlI
were
synthesized
using
AlI
3
or
)]Li(OEt
)],
respectively,
structurally
characterized.
While
reduction
with
KC
8
led
merely
unidentified
products,
dehalogenation
afforded
dimer
desired
{[Si
)]Al:}
aluminylene
a
four‐membered
Si
IV
Al
III
ring.
Remarkably,
proposed
intermediates
]Al
could
be
produced
through
reaction
Collman's
reagent,
K
Fe(CO)
4
,
trapped
as
:→Fe(CO)
5
6
respectively.
is
stable
in
solution,
loses
one
CO
solution
afford
silylene‐
aluminylene‐coordinated
iron(0)
complex
7
from
an
intramolecular
substitution
reaction.
electronic
structures
novel
compounds
investigated
by
Density
Functional
Theory
calculations.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 9, 2025
The
salt
metathesis
reaction
involving
a
diamine-based
antimony
chloride
precursor
with
sodium
arsaethynolate
in
the
presence
of
PMe3
leads
to
formation
stibanyl-functionalized
PMe3-arsinidene
(2).
Detailed
analyses
through
single-crystal
X-ray
diffraction
and
density
functional
theory
2
confirm
covalent
Sb-As
bonds
reveal
its
polarized
nature
multiple-bond
character.
In
contrast
complex
2,
substituting
xylyl
isocyanide
or
1,3-diisopropyl-4,5-dimethyl-imidazolin-2-ylidene
(IiPr)
produces
an
isocyanide-arsinidene
adduct
(3)
IiPr-arsaketene
(4),
respectively.
Furthermore,
related
reactions
1
phosphaethynolate
yield
both
stibanyl-phosphaketene
(5)
IiPr-phosphaketene
(6).
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
The
di-NHCs-stabilized
stannyliumylidene
serves
as
an
efficient
pre-catalyst
for
the
selective
hydrosilylation
of
CO
2
to
silyl
formate.
Experimental
mechanistic
studies
and
quantum
chemical
calculations
revealed
mechanism.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 28, 2025
Abstract
Copper
is
ubiquitous
as
a
structural
material,
and
reagent
in
(bio)chemical
transformations.
A
vast
number
of
chemical
reactions
rely
on
the
near-inevitable
preference
copper
for
positive
oxidation
states
to
make
useful
compounds.
Here
we
show
this
electronic
paradigm
can
be
subverted
stable
compound
with
copper-magnesium
bond,
which
conforms
formal
state
Cu(-I).
The
Cu-Mg
bond
synthesized
by
reaction
an
N-heterocyclic
carbene
(NHC)
ligated
alkoxide
dimeric
magnesium(I)
compound.
Its
identity
confirmed
single-crystal
X-ray
analysis
NMR
spectroscopy,
computational
investigations
provide
data
consistent
high
charge
density
at
copper.
acts
source
cupride
anion,
transferring
NHC-copper
fragment
electrophilic
s-,
p-,
d-block
atoms
known
new
copper-containing
