The
chemistry
of
low-valent
bismuth
compounds
has
recently
unlocked
new
concepts
in
catalysis
as
well
unique
electronic
structure
fundamentals.
In
this
work,
we
describe
the
synthesis
and
characterization
a
highly-reduced
salt
featuring
cationic
core
based
on
three
contiguous
Bi(I)
centers.
triatomic
bismuth-based
holds
an
situation
that
mimics
description
archetypical
carbonbased
π-allyl
cation.
Structural,
spectroscopic
theoretical
analyses
validate
π-delocalization
between
bismuth’s
highly
diffused
6p-orbitals,
resulting
1.5
bond
order
Bi
atoms.
This
places
complex
heaviest
non-radioactive
cation
periodic
table.
Furthermore,
demonstrate
newly
synthesized
is
able
to
act
synthon
for
transfer
forge
other
organobismuth
complexes.
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.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(24)
Опубликована: Фев. 27, 2023
Key
challenges
in
modern
synthetic
chemistry
include
the
design
of
reliable,
selective,
and
more
sustainable
methods,
as
well
development
promising
candidates
for
new
materials.
Molecular
bismuth
compounds
offer
valuable
opportunities
they
show
an
intriguing
spectrum
properties
that
is
yet
to
be
fully
exploited:
a
soft
character,
rich
coordination
chemistry,
availability
broad
variety
oxidation
states
(at
least
+V
-I)
formal
charges
+3
-3)
at
Bi
atoms,
reversible
switching
between
multiple
states.
All
this
paired
with
status
non-precious
(semi-)metal
good
tendency
towards
low
toxicity.
Recent
findings
some
these
only
come
into
reach,
or
can
substantially
optimized,
when
charged
are
specifically
addressed.
In
review,
essential
contributions
synthesis,
analyses,
utilization
ionic
highlighted.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 6, 2025
Herein,
we
report
the
isolation
of
pyridine
moiety-functionalized
SiNSi
pincer-based
bis-silylene
ligand
(1)
and
its
reactivity
toward
various
halide
precursors
(X
=
Br
I)
group
13
elements
(M
Al,
Ga,
In).
This
gave
us
straightforward
access
to
pincer-coordinated
cations
(2–7).
These
complexes
are
duly
characterized
by
single-crystal
X-ray
diffraction
studies,
multinuclear
magnetic
resonance
spectroscopy
(1H,
13C,
29Si),
high-resolution
mass
spectrometry
techniques.
Their
electronic
properties
were
further
analyzed
with
help
quantum
chemical
calculations.
Chemical Science,
Год журнала:
2023,
Номер
14(17), С. 4549 - 4563
Опубликована: Янв. 1, 2023
Geometric
deformation
in
main
group
compounds
can
be
used
to
elicit
unique
properties
including
strong
Lewis
acidity.
Here
we
report
on
a
family
of
planar
bismuth(iii)
complexes
(cf.
typically
pyramidal
structure
for
such
compounds),
which
show
geometric
acidity
that
further
tuned
by
varying
the
steric
and
electronic
features
triamide
ligand
employed.
The
structural
dynamism
bismuth
was
probed
both
solid
solution
phase,
revealing
at
least
three
distinct
modes
intermolecular
association.
A
modified
Gutmann-Beckett
method
assess
their
electrophilicity
employing
trimethylphosphine
sulfide
addition
triethylphosphine
oxide
as
probes,
providing
insights
into
preference
binding
hard
or
soft
substrates.
Experimental
studies
were
complemented
computational
assessment
affinities
dissection
latter
intrinsic
bond
strength
energy
components.
results
comparable
triarylboranes,
with
added
ability
bind
two
bases
simultaneously,
reduced
discrimination
against
We
also
study
catalytic
efficacy
these
ring
opening
polymerization
cyclic
esters
ε-caprolactone
rac-lactide.
polymers
obtained
excellent
dispersity
values
high
molecular
weights
low
catalyst
loadings
used.
retain
performance
under
industrially
relevant
conditions,
suggesting
they
may
useful
less
toxic
alternatives
tin
catalysts
production
medical
grade
materials.
Collectively,
establish
not
only
novel
neutral
platform
acidity,
but
potentially
valuable
one
catalysis.
Nature Chemistry,
Год журнала:
2025,
Номер
17(2), С. 265 - 270
Опубликована: Янв. 6, 2025
Abstract
The
chemistry
of
low-valent
bismuth
compounds
has
recently
unlocked
new
concepts
in
catalysis
and
unique
electronic
structure
fundamentals.
In
this
work,
we
describe
the
synthesis
characterization
a
highly
reduced
salt
featuring
cationic
core
based
on
three
contiguous
Bi(I)
centres.
triatomic
bismuth-based
exhibits
an
configuration
that
mimics
canonical
description
archetypical
carbon-based
π
-allyl
cation.
Structural,
spectroscopic
theoretical
analyses
validate
-delocalization
between
bismuth’s
diffused
6
p
orbitals,
resulting
bonding
situation
which
atoms
are
interconnected
by
two
bonds,
formally
possessing
1.5
bond
order
each.
This
defines
complex
as
heaviest
stable
cation
periodic
table.
Furthermore,
demonstrate
newly
synthesized
is
able
to
act
synthon
for
transfer
forge
other
organobismuth
complexes.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 16, 2025
The
work
establishes
the
salt
of
a
tetra-cationic
distibane,
[L2Sb2][CF3SO3]4
=
[1]2[OTf]4
(CF3SO3
OTf),
stabilized
by
bis(α-iminopyridine)
ligand
L,
defying
Coulombic
repulsion.
synthetic
approach
involved
dehydrocoupling
reaction
when
mixture
L
and
Sb(OTf)3
in
1:1
ratio
was
treated
with
Et3SiH/LiBEt3H
as
hydride
source.
Compound
also
achieved
from
[LSbCl][OTf]2
precursor
using
Et3SiH.
Dissolution
polar
solvents
unveiled
formation
persistent
L-stabilized
dicationic
Sb(II)
radical
monomer
[1][OTf]2,
while
addition
Me3SiOTf
regenerated
dimer
[1]2[OTf]4.
homolytic
cleavage
Sb–Sb
bond
[1]24+
has
manifested
exchange
reactions
between
Ph2Ch2
(Ch
S,
Se),
giving
[LSb(SPh)][OTf]2
[2][OTf]2
[LSb(SePh)][OTf]2
[3][OTf]2,
respectively,
acetonitrile.
Reaction
p-benzoquinone
gave
[L2Sb2(C6H4O2)][OTf]4
[4][OTf]4.
An
interesting
oxygen
atom
insertion
occurred
2,2,6,6-tetramethylpiperidine-1-oxyl
(TEMPO)
to
give
[L2Sb2O][
OTf]4
[5][OTf]4.
oxo-bridged
compound
[5][OTf]4
obtained
exposure
open
air.
strong
Mn–Mn
[Mn2(CO)10]
could
be
cleaved
reacting
presence
pyridine
form
[LSbMn(CO)5][
OTf]2
[6][OTf]2.
On
other
hand,
[Co2(CO)8]
oxidative
product
[L2Sb2Co(CO)3][OTf]3
[7][OTf]3.
compounds
were
characterized
both
solid
solution
states.
Computational
studies
comprehensive
understanding
experimental
findings.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(30)
Опубликована: Март 8, 2023
Abstract
The
molecular
compound
[BiDipp
2
(SbF
6
)],
containing
the
bulky,
donor‐free
bismuth
cation
]
+
has
been
synthesized
and
fully
characterized
(Dipp=2,6‐
i
Pr
‐C
H
3
).
Using
its
methyl
analog
[BiMe
)]
as
a
second
reference
point,
impact
of
steric
bulk
on
bismuth‐based
Lewis
acidity
was
investigated
in
combined
experimental
(Gutmann‐Beckett
modified
Gutmann‐Beckett
methods)
theoretical
approach
(DFT
calculations).
Reactivity
studies
cations
towards
[PF
−
neutral
bases
such
isocyanides
C≡NR’
revealed
facile
fluoride
ion
abstraction
straightforward
pair
formation,
respectively.
first
examples
compounds
featuring
bismuth‐bound
have
isolated
characterized.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(17)
Опубликована: Март 7, 2024
Abstract
“How
strong
is
this
Lewis
acid?”
a
question
researchers
often
approach
by
calculating
its
fluoride
ion
affinity
(FIA)
with
quantum
chemistry.
Here,
we
present
FIA49k,
an
extensive
FIA
dataset
48,986
data
points
calculated
at
the
RI‐DSD‐BLYP‐D3(BJ)/def2‐QZVPP//PBEh‐3c
level
of
theory,
including
13
different
p
‐block
atoms
as
accepting
site.
The
FIA49k
was
used
to
train
FIA‐GNN,
two
message‐passing
graph
neural
networks,
which
predict
gas
and
solution
phase
values
molecules
excluded
from
training
mean
absolute
error
14
kJ
mol
−1
(
r
2
=0.93)
SMILES
string
acid
only
input.
accuracy
notable,
given
wide
energetic
range
750
spanned
FIA49k.
model's
value
demonstrated
four
case
studies,
predictions
for
extracted
Cambridge
Structural
Database
reproducing
results
catalysis
research
available
in
literature.
Weaknesses
model
are
evaluated
interpreted
chemically.
FIA‐GNN
can
be
reached
via
free
web
app
www.grebgroup.de/fia‐gnn
).
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(34)
Опубликована: Июнь 30, 2023
Abstract
Bent
(hetero)allenes
such
as
carbodicarbenes
and
carbodiphosphoranes
can
act
neutral
C‐donor
ligands,
diverse
applications
in
coordination
chemistry
have
been
reported.
N‐Heterocyclic
diazoolefins
are
heterocumulenes,
which
function
a
similar
fashion
L‐type
ligands.
Herein,
we
describe
the
synthesis
reactivity
of
an
anionic
diazoolefin.
This
compound
displays
distinct
compared
to
diazoolefins,
evidenced
by
preparation
diazo
compounds
via
protonation,
alkylation,
or
silylation.
The
diazoolefin
be
employed
ambidentate,
X‐type
ligand
salt
metathesis
reactions
with
metal
halide
complexes.
Extrusion
dinitrogen
was
observed
reaction
PCl(N
i
Pr
2
)
,
resulting
stable
phosphinocarbene.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 19, 2024
Low-valent
antimony
and
bismuth
have
emerged
as
novel
platforms
for
achieving
reversible
small-molecule
activation
at
main-group
metals.
Although
various
examples
of
oxidative
addition
reactions
monomeric
Sb(I)
Bi(I)
been
reported,
the
chemistry
heavy
group
15
Sb(I)═Sb(I)/Bi(I)═Bi(I)
double
bonds
toward
small
molecules
remains
largely
unexplored.
In
this
study,
we
present
a
straightforward
synthesis
distibene
dibismuthene
dications
coordinated
with
neutral
carbodiphosphorane
(CDP)
ligand.
The
nonbonding
interactions
between
occupied
p-orbital
CDP
ligand
π-bonding
orbital
Sb═Sb/Bi═Bi
yield
compounds
exceptionally
HOMO-LUMO
gaps.
addition,
reduction
steric
hindrance
compared
to
known
derivatives
stabilized
bulky
aryl
groups
allows
better
accessibility
bonds.
This
high
reactivity
is
demonstrated
in
diphenyldisulfide
well
[2+2]
cycloadditions
alkynes.
Additionally,
Sb═Sb
bond
reversibly
adds
2,3-dimethylbutadiene
[4+2]
cycloaddition
reaction.
