Dicationic 1-Germa and 1-Stannavinylidenes: Synthesis, Structure, and Reactivity
JACS Au,
Journal Year:
2025,
Volume and Issue:
5(3), P. 1289 - 1298
Published: Feb. 19, 2025
The
synthesis
of
heteronuclear
vinylidene
analogues
containing
heavier
group
14
elements
(R2C═E:,
E
=
Si,
Ge,
Sn)
has
been
a
challenging
task
due
to
their
inherent
instability.
In
this
study,
we
report
the
dicationic
1-germavinylidene
(3Ge)
and
1-stannavinylidene
(3Sn)
by
using
sym-bis(2-pyridyl)-tetraphenylcarbodiphosphorane
(CDPPy2)
as
donor
ligand.
Both
3Ge
3Sn
have
characterized
single-crystal
X-ray
diffraction
analysis,
NMR
spectroscopy,
high-resolution
mass
spectrometry.
structural
supported
results
theoretical
calculations,
confirms
that
feature
polarized
C═E
double
bond
lone
pair
electrons
located
at
atom
(E
Ge
Sn).
reactions
with
IDippMCl
(M
Cu,
Ag,
Au)
give
M–Cl
addition
products.
Mechanistic
studies
on
activation
Au–Cl
demonstrate
its
ambiphilicity.
This
work
represents
an
example
utilization
carbone
ligand
both
σ
π
for
analogues.
Language: Английский
Synthesis and redox catalysis of Carbodiphosphorane ligated stannylene
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Nov. 14, 2024
Heavier
group
14
carbene
analogues,
exhibiting
transition-metal-like
behavior,
display
remarkable
capability
for
small
molecule
activation
and
coordination
chemistry.
However,
their
application
in
redox
catalysis
remains
elusive.
In
this
paper,
we
report
the
synthesis
isolation
of
a
stannylene
with
carbodiphosphorane
ligand.
The
nucleophilic
reactivity
at
divalent
tin
center
is
elucidated
by
computational
studies.
Moreover,
exhibits
catalytic
activity
hydrodefluorination
reaction
fluoroarenes.
Mechanistic
investigations
into
elementary
steps
confirm
Sn
Language: Английский