Organometallics,
Journal Year:
2024,
Volume and Issue:
43(22), P. 2906 - 2915
Published: Nov. 14, 2024
Four
distinct
organotin(IV)
compounds,
[R2Sn(L1)]
[R
=
Ph
(1)
and
n-Bu
(2)]
[R2Sn(L2)]
(3)
(4)],
have
been
synthesized
from
two
polydentate
proligands
such
as
2-((2-hydroxy-3-methoxybenzylidene)amino)-4-methyl
phenol
(H2L1)
4-(tert-butyl)-2-(((2-hydroxy-5-methylphenyl)imino)methyl)phenol
(H2L2).
The
compounds
were
by
the
reaction
of
halides
Ph2SnCl2
(n-Bu)2SnCl2
with
both
using
Et3N
a
base.
All
fully
characterized
FT-IR
spectroscopy;
1H,
13C{1H},
119Sn
NMR
HRMS
spectrometry;
single-crystal
X-ray
diffraction
analysis.
Lewis
acidity
all
was
determined
Gutmann–Beckett
method.
catalytic
activities
investigated
for
synthesis
naphthofurans
trans-β-nitrostyrene
derivatives
β-naphthol
or
α-naphthol
under
solvent-free
conditions.
maximum
yield
is
up
to
95%.
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.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(12), P. 6150 - 6243
Published: Jan. 1, 2024
We
have
compiled
the
recent
progress
of
low-valent
group-14
compounds
in
catalysis,
polymerization,
small
molecule
activation,
thin
film
deposition,
photophysical
properties,
and
medicinal
properties.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 29, 2025
Nitrenes
(R–N)
have
been
subject
to
a
large
body
of
experimental
and
theoretical
studies.
The
fundamental
reactivity
this
important
class
transient
intermediates
has
attributed
their
electronic
structures,
particularly
the
accessibility
triplet
vs
singlet
states.
In
contrast,
structure
trends
along
heavier
pnictinidene
analogues
(R–Pn;
Pn
=
P–Bi)
are
much
less
systematically
explored.
We
here
report
synthesis
series
metallodipnictenes,
{M–Pn═Pn–M}
(M
PdII,
PtII;
P,
As,
Sb,
Bi)
characterization
metallopnictinidene
intermediates,
{M–Pn}
for
Sb.
Structural,
spectroscopic,
computational
analysis
revealed
spin
ground
states
metallopnictinidenes
with
characteristic
series.
comparison
nitrene,
pnictinidenes
exhibit
lower-lying
state
SOMOs
excited
states,
thus
suggesting
increased
electrophilic
reactivity.
Furthermore,
splitting
magnetic
microstates
is
beyond
phosphinidenes
{M–P}
dominated
by
heavy
pnictogen
atom
induced
spin–orbit
coupling.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(19), P. 9738 - 9831
Published: Jan. 1, 2024
Developments
in
synthetic
methods
for
and
reactivity
of
heavier
tetrylene
tetrylyne
complexes
the
d-block
elements
are
summarised,
with
a
view
towards
cooperative
bond
activation
utilisation
catalysis.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(21), P. 2902 - 2905
Published: Jan. 1, 2024
The
electron-rich
acyclic
germylene
LGa(μ–Cl)GeAr
Mes
(1)
activates
unpolar
bonds
as
is
shown
in
oxidative
addition
reactions
with
H
2
and
P
4
,
yielding
L(Cl)GaGe(H)
Ar
(2)
L(Cl)Ga(P
)GeAr
(3).
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 7, 2025
The
chemistry
of
heterocycles
containing
"diaza"
units
has
been
extensively
studied
due
to
their
applications
ranging
from
pharmaceuticals
advanced
materials.
In
contrast,
incorporating
heavier
elements,
such
as
Sb
and
Bi,
remain
exceedingly
rare
lack
straightforward
synthetic
methodologies.
Herein,
we
present
a
comprehensive
experimental
theoretical
investigation
the
first
diazadistiboylidenes
(1a,
1b),
synthesized
via
[3
+
2]-cycloaddition
between
distibene
diazoolefins.
These
stiboylidenes
are
key
intermediates
promote
selective
nucleophilic
substitution,
leading
example
diantimonyl
anion.
Furthermore,
upon
visible-light
irradiation,
could
isolate
methylenedistibiranes,
analogs
methylenediaziridine
(C2H4N2).
findings
offer
novel
platform
for
heavy
dipnictogen
chemistry,
showcasing
that
diazoolefins,
in
combination
with
visible
light,
can
facilitate
formation
unprecedented
serve
CO2
activation.
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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(43), P. 29877 - 29882
Published: Oct. 18, 2024
Complexation
of
the
green
bismuthinidene
(RBi)
with
two
equivalents
a
highly
fluorinated
aryl
iodide
at
low
temperature
allows
crystallographic
identification
an
unstable
red
species
that
can
be
regarded
as
intermediate
in
overall
Bi(I)
→
Bi(III)
oxidation
process.
Both
C-I
bonds
are
orientated
toward
filled
6p
orbital
bismuth
(Bi-I
distances
3.44-3.52
Å),
leading
to
elongation
by
0.05
and
0.07
Å.
Density
functional
theory
(DFT)
calculations
confirm
center
is
indeed
acting
electron
donor,
establishing
strong
directional
halogen
bonds.
The
color
change
from
upon
bond
formation
consequence
energetic
stabilization
lone
pair
interactions
sigma-holes
donors.
Overall,
this
study
presents
first
structural
proof
bismuth,
more
generally
heavy
organopnictogen(I)
compounds,
acceptors.
