Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(42), P. 6399 - 6402
Published: Jan. 1, 2023
Half
a
century
after
the
photolytic
disproportionation
of
Lappert's
dialkyl
stannylene
SnR2,
R
=
CH(SiMe3)2
(1)
gave
persistent
trivalent
radical
[˙SnR3],
characterization
corresponding
Sn(I)
product,
˙SnR
is
now
described.
It
was
isolated
as
hexastannaprismane
Sn6R6
(2),
from
reduction
1
by
Mg(I)-reagent,
Mg(BDIDip)2
(BDI
(DipNCMe)2CH,
Dip
2,6-diisopropylphenyl).
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(20)
Published: March 5, 2024
Abstract
Lead‐based
radicals
in
the
oxidation
state
of
+1
are
elusive
species
and
highly
challenging
to
isolate
condensed
phase.
In
this
study,
we
present
synthesis
characterization
first
isolable
free
plumbylyne
radical
2
bearing
a
one‐coordinate
Pb(I)
atom.
It
reacts
with
an
N
‐heterocyclic
carbene
(NHC)
afford
two‐coordinate
NHC‐ligated
3
.
represent
Pb(I)‐based
radicals.
Theoretical
calculations
electron
paramagnetic
resonance
analysis
revealed
that
unpaired
mainly
resides
at
Pb
6p
orbital
both
Owing
unique
nature
atom
,
it
possesses
two‐fold
pseudo‐degeneracy
substantial
unquenched
angular
momentum,
exhibits
hitherto
strongest
g
‐factor
anisotropy
(
x,y,z
=1.496,
1.166,
0.683)
amongst
main
group
Preliminary
investigations
into
reactivity
unveiled
its
Pb‐centered
nature,
plumbylenes
were
isolated
as
products.
Research Square (Research Square),
Journal Year:
2024,
Volume and Issue:
unknown
Published: April 11, 2024
Abstract
Mono-coordinated
metallyenes
(R–M:)
of
the
Group
13
elements
feature
a
non-bonding
pair
electrons
together
with
two
vacant
orbitals,
which
makes
them
highly
reactive
ambiphiles
that
readily
activate
small
molecules
by
oxidative
addition.
In
consequence
their
pronounced
reactivity,
examples
mono-coordinated
organometallics
aluminium(I)
and
gallium(I)
remain
rare.
Here,
we
report
one-step
synthesis
monomeric
compound
undergoes
addition
reactions
and,
more
remarkably,
carbometalation
alkynes
retention
low
oxidation
state
+I
coordination
number
one
at
gallium.
This
contrasts
previous
reports
on
reactivity
low-valent
main-group
compounds,
are
regularly
oxidized
to
compounds
in
stable
higher
state.
These
findings
provide
new
approach
access
pave
way
for
development
novel
bond-functionalisation
strategies
hence
could
enable
catalytic
processes
future.
Research Square (Research Square),
Journal Year:
2024,
Volume and Issue:
unknown
Published: June 14, 2024
Abstract
Free
nitrenes
of
R–N
are
short-lived
intermediates
in
a
variety
nitrogen-involved
transformations.
They
feature
either
singlet
ground
state
or
triplet
state,
depending
on
the
electronic
properties
substituents
R.
Triplet
arylnitrenes
typically
undergo
facile
ring
expansion
to
azacycloheptatetraenes,
making
their
isolation
condensed
phase
highly
challenging.
Herein,
we
present
synthesis,
and
characterization
an
isolable
arylnitrene
supported
by
bulky
hydrindacene
ligand.
The
high
stability
is
largely
attributed
sufficient
steric
hindrance
effective
electron
delocalization
imparted
supporting
Electron
paramagnetic
resonance
spectroscopy
conjunction
with
correlated
wavefunction
based
ab
initio
calculations
unambiguously
demonstrated
its
axial
zero-field
splitting
D
=
0.92
cm–1
vanishing
rhombicity
E/D
0.002.
This
work
not
only
presents
long-sought
reaction
intermediate,
but
also
provides
in-depth
insights
into
mechanisms
involving
nitrenes.
