Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(41)
Published: July 11, 2024
Establishing
unprecedented
types
of
bonding
interactions
is
one
the
fundamental
challenges
in
synthetic
chemistry,
paving
way
to
new
(electronic)
structures,
physicochemical
properties,
and
reactivity.
In
this
context,
unsupported
element-element
are
particularly
noteworthy
since
they
offer
pristine
scientific
information
about
newly
identified
structural
motif.
Here
we
report
synthesis,
isolation,
full
characterization
heterobimetallic
Bi/Pt
compound
[Pt(PCy
New Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
48(12), P. 5523 - 5529
Published: Jan. 1, 2024
New
hypercoordinated
organopnictogen(
iii
)
bis(aryloxides),
ArPn(SC
6
H
3
R
2
-2,6)
(Pn
=
Sb,
Bi;
Ar
NCN-pincer
ligand;
i
Pr,
OMe),
have
been
prepared
and
their
solution
solid
state
structures
investigated.
Synlett,
Journal Year:
2023,
Volume and Issue:
unknown
Published: Oct. 6, 2023
Abstract
Recent
advances
in
the
isolation
of
tamed
bismuth
radicals
and
selective
situ
generation
highly
reactive
have
set
stage
for
application
these
compounds
organic
organometallic
synthesis
catalysis.
Here,
we
provide
a
summary
methodological
approaches
field.
Important
strategies
accessing
radical
species
are
presented
key
examples
their
applications
outlined,
highlighting
how
this
class
has
emerged
as
new
valuable
tools
synthetic
practitioners.
1
Introduction
2
Generation
Bismuth
Radical
Species
by
Homolysis
2.1
Temperature-Induced
2.2
Light-Induced
2.3
Light-/Temperature-Induced
Bi–C
Polar
Oxidative
Addition
Complexes
3
Applications
Bismuth-Centered
Organic
Synthesis
3.1
Bismuth-Catalyzed
Cycloisomerization
Iodo
Olefins
3.2
Controlled
Polymerization
Reactions
3.3
Bismuth-Promoted
Pn–Pn
C–S
Coupling
3.4
Dehydrocoupling
Silanes
with
TEMPO
3.5
C–N
Redox-Active
Electrophiles
3.6
Giese-Type
3.7
Aryl
to
Photoactive
Bismuthinidenes
4
Conclusions
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(68)
Published: Aug. 31, 2023
The
synthesis
and
first
structural
characterization
of
the
[K(18-crown-6)]
bismolyl
Bitet
(C4
Me4
Bi)
contact
ion
pair
(1)
is
presented.
Notably,
according
to
Natural
Resonance
Theory
calculations,
anion
1
features
two
types
leading
mesomeric
structures
with
localized
anionic
charge
lone
pairs
electrons
at
BiI
center,
as
well
delocalized
in
π-conjugated
C4
Bi
ring.
enable
a
unique
bridging
coordination
mode
ligand,
shown
for
rare
earth
metal
complex
(Cptet2
Y)2
(μ-η1
-Bitet
)2
(2).
latter
results
from
salt
metathesis
reaction
KBitet
Cptet2
Y(BPh4
)
(Cptet
=C5
H).
Y-Bi
bonding
interaction
2
16.6
%
covalency
yttrium
remarkably
large.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(36), P. 14837 - 14843
Published: Jan. 1, 2024
The
syntheses
of
first,
extremely
sensitive
donor-stabilized
monomeric
bismuthanylboranes
D·BH
2
Bi(SiMe
3
)
(D
=
NHC,
DMAP)
and
the
bismuthanylgallane
IDipp·GaH
are
presented
representing
unique
element
combinations
bismuth
triels.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(32), P. 22122 - 22128
Published: Aug. 5, 2024
The
discovery
and
utilization
of
main-group
element
catalysts
that
behave
similarly
to
transition
metal
(TM)
complexes
have
become
increasingly
active
areas
investigation
in
recent
years.
Here,
we
report
a
series
Lewis
acidic
bismuth(III)
allow
for
the
catalytic
allylic
C(sp3)–H
functionalization
olefins
via
an
organometallic
complexation-assisted
deprotonation
mechanism
generate
products
containing
new
C–C
bonds.
This
heretofore
unexplored
mode
reactivity
was
applied
regioselective
1,4-dienes
allylbenzene
substrates.
Experimental
computational
mechanistic
studies
support
key
steps
proposed
cycle,
including
intermediacy
elusive
Bi–olefin
allylbismuth
species.
Main-group
metals
as
supporting
ligands
for
transition
offer
potential
bimetallic
synergistic
effects.
We
investigated
a
bismuth-palladium
system
utilizing
PBiP
pincer
ligand
(BiPdCl)
precatalysts
electrocatalytic
proton
reduction
with
thiophenol.
Rinse
tests
revealed
the
formation
of
surface-bound
active
species,
likely
comprised
Pd-based
heterogenous
materials.
NMR
and
UV-visible
spectroscopic
studies
unveiled
that
in
diluted
solutions
polar
coordinating
solvents,
chloride
trans
to
bismuthane
readily
dissociates,
affording
solvent-coordinated
species
(BiPdsolvent)
predominant
solution
species.
Following
thiol–
solvent
exchange,
an
equilibrium
mixture
solvent-bound
thiolate
complex
(BiPdS)
forms.
The
crystal
structures
BiPdS
acetonitrile-coordinated
model
(BiPdAcN)
shows
thermodynamic
influence
ligand.
Structural
analysis,
corroborated
by
computational
investigations,
suggests
BiPdsolvent
is
primarily
ligand-based
than
Pd-centered,
hinting
at
Bi(III)–Pd(0)
oxidation
states
rather
Bi(I)–Pd(II)
suggested
Lewis
structure
BiPdsolvent.
electron-rich
Pd
electron-poor
Bi
centers
explain
its
electrochemical
decomposition
similar
other
Pd(0)
Our
findings
shed
light
on
electronic
properties
reactivities
studied
Bi–Pd
compounds,
offering
example
ambiguous
within
this
system.
Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(44), P. 18228 - 18238
Published: Oct. 23, 2023
The
first
series
of
9-bisma-10-pnictatriptycenes
Bi(C6H4)3Pn
(2-Pn,
Pn
=
P-Bi;
see
graphic)
has
been
synthesized
in
a
two-step
procedure
via
suitable
tris(2-bromophenyl)pnictanes
1-Pn
and
characterized
solution
as
well
the
solid
state.
DFT
calculations
suggest
preferential
interactions
between
2-Pn
soft
Lewis
acids
lighter
pnictogen
donor
atom.
Experimental
studies
demonstrate
that
even
weakest
base
2-Pn,
namely
dibismatriptycene
2-Bi,
interacts
with
acidic
[BiMe2(SbF6)]
solution.
Analytical
techniques
include
(VT-)NMR
spectroscopy,
DOSY
NMR
high-resolution
mass
spectrometry,
single-crystal
X-ray
diffraction
analyses,
calculations.
