Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
30(11)
Published: Dec. 20, 2023
Abstract
When
bismuth
atoms
are
incorporated
into
cyclic
organic
systems,
this
commonly
goes
along
with
strained
or
distorted
molecular
geometries,
which
can
be
exploited
to
modulate
the
physical
and
chemical
properties
of
these
compounds.
In
six‐membered
heterocycles,
often
accompanied
by
oxygen,
sulfur
nitrogen
as
a
second
hetero‐element.
work,
we
present
first
examples
rings,
in
two
CH
units
replaced
BiX
moieties
(X=Cl,
Br,
I),
resulting
dihydro‐anthracene
analogs.
Their
behavior
chemically
reversible
reduction
reactions
is
explored,
aiming
at
generation
dibisma‐anthracene
(bismanthrene).
Heterometallic
compounds
(Bi/Fe,
Bi/Mn)
introduced
potential
bismanthrene
surrogates,
supported
bismanthrene‐transfer
selenium.
Analytical
techniques
used
investigate
reported
include
NMR
spectroscopy,
high‐resolution
mass
spectrometry,
single‐crystal
X‐ray
diffraction
analyses,
DFT
calculations.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(24)
Published: Feb. 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.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(52), P. 8043 - 8058
Published: Jan. 1, 2023
Recent
advances
in
the
activation
of
small
molecules
with
well-defined
molecular
compounds
heavy
p-block
elements
(with
a
principle
quantum
number
n
>
4)
are
summarized,
highlighting
key
strategies,
challenges,
and
opportunities.
Inorganic Chemistry,
Journal Year:
2022,
Volume and Issue:
61(46), P. 18640 - 18652
Published: Nov. 9, 2022
We
report
a
comprehensive
assessment
of
Lewis
acidity
for
series
carbone-stibenium
and
-bismuthenium
ions
using
the
Gutmann-Beckett
(GB)
method.
These
new
antimony
bismuth
cations
have
been
synthesized
by
halide
abstractions
from
(CDC)PnBr3
[(pyCDC)PnBr2][Br]
(CDC
=
carbodicarbene;
Pn
Sb
or
Bi;
py
pyridyl).
The
reaction
(CDC)SbBr3
(1)
with
one
two
equivalents
AgNTf2
(NTf2
bis(trifluoromethanesulfonyl)imide)
AgSbF6
gives
stibaalkene
mono-
dications
form
[(CDC)SbBr3-n][A]n
(2-4;
n
1,2;
A
NTf2
SbF6).
trication
[(CDC)2Sb][NTf2]3
(5)
was
also
isolated
collectively
these
molecules
fill
gap
among
cationic
pnictaalkenes.
are
compared
to
related
CDC-bismaalkene
complexes
6-9.
With
goal
preparing
highly
acidic
compounds,
tridentate
bis(pyridine)carbodicarbene
(pyCDC)
used
as
ligand
access
(10,
12)
trications
[(pyCDC)Pn][NTf2]3
(Pn
(11),
Bi
(13)),
forgoing
need
second
CDC
in
synthesis
5.
bonding
situation
is
elucidated
through
electron
density
energy
decomposition
analyses
combination
natural
orbital
chemical
valence
theory.
In
each
complex,
there
exists
CDC-Pn
double
interaction,
consisting
strong
σ-bond
weaker
π-bond,
whereby
π-bond
gradually
strengthens
increase
charge
complex.
Notably,
[(CDC)SbBr][NTf2]2
(4)
has
an
acceptor
number
(AN)
(84)
that
comparable
quintessential
acids
such
BF3,
tricationic
pnictaalkene
11
13
exhibit
ANs
109
Sb)
84
Bi),
respectively,
which
highest
values
reported
any
cation.
Moreover,
calculated
fluoride
ion
affinities
(FIAs)
99.8
94.3
kcal/mol,
larger
than
SbF5
(85.1
kcal/mol),
suggest
superacids.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(30)
Published: March 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.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(19), P. 5214 - 5219
Published: Jan. 1, 2023
CO
2
and
CS
cleanly
insert
into
Bi–N
bonds
of
cationic
bismuth
amides.
The
insertion
products
are
metastable
undergo
either
elimination
along
with
CH
activation
or
light-induced
bismuth(
i
)
triflate
C–S
bond
formation.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(50), P. 7755 - 7758
Published: Jan. 1, 2023
Salt
metathesis
of
L(TfO)Ga-substituted
dipnictenes
allowed
for
the
synthesis
heavy
dipnictene
dications,
which
can
be
considered
as
isoelectronic
analogues
butadiene
dication.
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
