Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(32), С. 17746 - 17754
Опубликована: Авг. 7, 2023
Anti-van't
Hoff-Le
Bel
configured
p-block
element
species
possess
intrinsically
high
reactivity
and
are
thus
challenging
to
isolate.
Consequently,
numerous
elements
in
this
configuration,
including
square-planar
germanium(IV),
remain
unexplored.
Herein,
we
follow
a
concept
reach
anti-van't
by
ligand
dissociation
from
rigid
calix[4]pyrrole
germane
its
bis(thf)
adduct.
While
the
macrocyclic
assures
coordination
uncomplexed
form,
labile
thf
donors
provide
robustness
for
isolation
on
multigram
scale.
Unique
properties
of
low-lying
acceptor
orbital
imparted
germanium(IV)
can
be
verified,
e.g.,
isolating
an
elusive
anionic
hydrido
germanate
exploiting
it
bond
activations.
Aldehydes,
water,
alcohol,
CN
triple
activated
first
time
germanium-ligand
cooperativity.
Unexpected
behaviors
against
fluoride
ion
disclose
critical
interferences
putative
redox-coupled
transfer
during
experimental
determination
Lewis
acidity.
Overall,
showcase
how
lability
grants
access
uncharted
chemistry
line
up
as
member
emerging
class
structurally
constrained
elements.
Inorganic Chemistry,
Год журнала:
2022,
Номер
61(48), С. 19452 - 19462
Опубликована: Ноя. 22, 2022
Bismuth
complexes
stabilized
by
carbon-based
donor
ligands
are
underserved
their
instability,
often
due
to
facile
ligand
dissociation
and
deleterious
protonolysis.
Herein,
we
show
that
the
ortho-bismuthination
of
hexaphenylcarbodiphosphorane
enables
a
robust
framework
with
geometrically
constrained
carbone-bismuth
bonding
interactions,
which
highly
tunable
cationization.
The
carbodiphosphorane
bismuth
halides
(1
2)
remarkably
air-stable
feature
unprecedented
transcarboneC-Bi-X
ligation,
resulting
in
elongated
Bi-X
bonds.
In
contrast
known
complexes,
hydrolytic
activation
carbone
yields
well-defined
organobismuth
subsequent
dehydrohalogenation
is
feasible
using
potassium
bis(trimethylsilyl)amide
or
N-heterocyclic
carbenes.
redox-flexibility
this
was
evaluated
high
catalytic
activity
1
2
for
silylation
2,2,6,6-tetramethylpiperidin-1-oxyl
(TEMPO)
under
mild
conditions
(50
°C,
24-96
h)
low
catalyst
loadings
(5-10
mol
%),
suggests
accessibility
short-lived
hydridic
radical
species.
reaction
1,
PhSiH3,
tris(pentafluorophenyl)borane
(BCF)
first
crystallographically
characterized
hydridoborate
complex
as
an
ionic
species
(9),
presumably
BCF-mediated
hydride
abstraction
from
unobserved
[Bi]-H
intermediate.
All
isolated
compounds
have
been
heteronuclear
NMR
spectroscopy
X-ray
crystallography,
situation
representative
(1,
2,
5,
9)
were
further
density
functional
theory.
Chemical Communications,
Год журнала:
2023,
Номер
59(66), С. 9918 - 9928
Опубликована: Янв. 1, 2023
The
icosahedral
carborane
cluster
can
accept
two
electrons
and
change
from
a
closed
closo
-form
to
an
open
nido
-form.
This
transformation
unlocks
the
potential
for
bond
activation
chemistry,
uranyl
capture,
stabilization
of
low-valent
centers.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(44), С. 24184 - 24190
Опубликована: Окт. 25, 2023
A
series
of
structurally
constrained
phosphenium
ions
based
on
pyridinylmethylamidophenolate
scaffolds
are
shown
to
undergo
P(III)/P(V)
oxidative
addition
with
C-H
bonds
alkynes,
alkenes,
and
arenes.
Nonactivated
substrates
such
as
benzene,
toluene,
deactivated
chlorobenzene
phosphorylated
in
quantitative
yields.
Computational
spectroscopic
studies
suggest
a
low-barrier
isomerization
from
bent
T-shaped
isomer
that
initiates
phosphorus-ligand-cooperative
pathway
subsequent
ring-chain
tautomerism.
Remarkably,
bond
activations
occur
reversibly,
allowing
for
reductive
elimination
back
P(III)
at
elevated
temperatures
or
the
exchange
other
substrates.
