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
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(8)
Published: Nov. 22, 2023
Abstract
Whereas
indications
of
radical
reactivity
in
bismuth
compounds
can
be
traced
back
to
the
19
th
century,
preparation
and
characterization
both
transient
persistent
bismuth‐radical
species
has
only
been
established
recent
decades.
These
advancements
led
emergence
field
chemistry,
mirroring
progress
seen
for
other
main‐group
elements.
The
seminal
fundamental
studies
this
area
have
ultimately
paved
way
development
catalytic
methodologies
involving
intermediates,
a
promising
approach
that
remains
largely
untapped
broad
landscape
synthetic
organic
chemistry.
In
review,
we
delve
into
milestones
eventually
present
state‐of‐the‐art
Our
focus
aims
at
outlining
intrinsic
discoveries
inorganic/organometallic
chemistry
contextualizing
their
practical
applications
synthesis
catalysis.
Accounts of Chemical Research,
Journal Year:
2023,
Volume and Issue:
56(9), P. 1018 - 1030
Published: April 17, 2023
ConspectusBismuth-based
research
has
become
a
highly
topical
field
in
recent
years,
yielding
remarkable
prospects
for
new
fundamental
insights
and
materials
applications,
ranging
from
innovative
catalysts
to
novel
pharmaceuticals,
due
this
heavy
metal's
virtually
nonradioactive
nontoxic
properties.
Given
that
the
6s2
electron
pair
can
be
stereochemically
active
under
certain
circumstances,
bismuth
atoms
adopt
variety
of
coordination
modes
bonding
environments
with
oxidation
states
(formally)
+V
-III.
As
consequence,
bismuth-based
compounds
cover
entire
spectrum
simple
much
more
unusual
cluster
cations
anions
exhibiting
metal-metal
homoatomic
manner,
or
concert
other
s-,
d-,
p-,
f-block
metal
atoms.
Such
clusters
show
high
potential
development
materials,
but
they
are
also
interesting
objects
by
themselves.
relatively
bismuth-rich
molecules,
deep
understanding
their
properties─including
unprecedented
structural
features,
complex
electronic
structures,
substantial
aromaticity,
as
well
formation
pathways─is
still
its
infancy.
The
topic
thus
spans
broad
range
sophisticated
synthetic
chemistry
through
interdisciplinary
experimental
theoretical
analyses
science.Based
on
our
work
several
notable
reports
groups,
article
will
highlight
successful
access
number
ions
emerging
both
solution-based
approaches
solid-state
chemistry.
It
shed
light
unique
properties
cause
chemical
physical
peculiarities
such
compounds.
Selected
examples
include,
not
limited
to,
(1)
first
encapsulation
actinide
intermetalloid
which
additionally
served
manifest
all-metal
π-aromaticity
(calculated)
record
ring
current
per
electron;
(2)
large
metalloid
{Zn12}
unit
stabilized
porphine-related
{Zn8Bi16}
moiety
[K2Zn20Bi16]6-;
(3)
largest
assembly
within
one
molecule,
observed
[{Ru(cod)}4Bi18]4-
consists
two
Bi-Bi-linked
"[{Ru(cod)}2Bi9]2-"
subunits.Notably,
growth
remained
largely
black
box,
is
starting
revealed,
however.
We
discuss
possible
pathways
(multi)metallic
nanoarchitectures
basis
smaller
subunits
were
detected
mass
spectrometric
could
captured
upon
reaction
organometallic
complexes.
In
addition
intrinsic
reviewed
herein,
we
briefly
introduce
usage
material
science
give
an
outlook
future
developments.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(35), P. 14202 - 14208
Published: Jan. 1, 2024
A
green
MOF
phosphor
can
maintain
84%
of
its
initial
emission
intensity
after
being
heated
to
150
°C,
exceeding
several
commercial
inorganic
phosphors.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(17), P. 4549 - 4563
Published: Jan. 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,
Journal Year:
2024,
Volume and Issue:
16(9), P. 1523 - 1530
Published: May 17, 2024
Abstract
Aromaticity
in
organic
molecules
is
well
defined,
but
its
role
metal-only
rings
remains
controversial.
Here
we
introduce
a
supramolecular
stabilization
approach
of
cationic
{Bi
4
}
rhomboid
within
the
symmetric
charge
sphere
two
bowl-shaped
dianionic
calix[4]pyrrolato
indinates.
Crystallographic
and
spectroscopic
characterization,
quantum
chemical
analysis
magnetically
induced
ring
currents
indicate
σ-aromaticity
formally
tetracationic
16-valence
electron
[Bi
]
4+
ring.
Computational
screening
for
other
p
-block
elements
identifies
planar
as
globally
preferred
structure
four-atomic
clusters.
The
aromatic
isoelectronic
to
[Al
4−
,
motif
previously
observed
antiaromatic
Li
3
−
gas
phase.
Thus,
subtle
factors
such
isotropy
seem
decide
over
aromaticity
or
antiaromaticity,
advising
caution
debates
based
on
Hückel
model—a
concept
valid
second-row
less
deterministic
heavier
congeners.
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.
