Transient Triplet Metallopnictinidenes M–Pn (M = PdII, PtII; Pn = P, As, Sb): Characterization and Dimerization
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 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.
Язык: Английский
Combining Distibene, Diazoolefins, and Visible Light: Synthesis and Reactivity of Inorganic Rings
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 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.
Язык: Английский
Tetra-Cationic Distibane Stabilized by Bis(α-iminopyridine) and Its Reactivity
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 16, 2025
The
work
establishes
the
salt
of
a
tetra-cationic
distibane,
[L2Sb2][CF3SO3]4
=
[1]2[OTf]4
(CF3SO3
OTf),
stabilized
by
bis(α-iminopyridine)
ligand
L,
defying
Coulombic
repulsion.
synthetic
approach
involved
dehydrocoupling
reaction
when
mixture
L
and
Sb(OTf)3
in
1:1
ratio
was
treated
with
Et3SiH/LiBEt3H
as
hydride
source.
Compound
also
achieved
from
[LSbCl][OTf]2
precursor
using
Et3SiH.
Dissolution
polar
solvents
unveiled
formation
persistent
L-stabilized
dicationic
Sb(II)
radical
monomer
[1][OTf]2,
while
addition
Me3SiOTf
regenerated
dimer
[1]2[OTf]4.
homolytic
cleavage
Sb–Sb
bond
[1]24+
has
manifested
exchange
reactions
between
Ph2Ch2
(Ch
S,
Se),
giving
[LSb(SPh)][OTf]2
[2][OTf]2
[LSb(SePh)][OTf]2
[3][OTf]2,
respectively,
acetonitrile.
Reaction
p-benzoquinone
gave
[L2Sb2(C6H4O2)][OTf]4
[4][OTf]4.
An
interesting
oxygen
atom
insertion
occurred
2,2,6,6-tetramethylpiperidine-1-oxyl
(TEMPO)
to
give
[L2Sb2O][
OTf]4
[5][OTf]4.
oxo-bridged
compound
[5][OTf]4
obtained
exposure
open
air.
strong
Mn–Mn
[Mn2(CO)10]
could
be
cleaved
reacting
presence
pyridine
form
[LSbMn(CO)5][
OTf]2
[6][OTf]2.
On
other
hand,
[Co2(CO)8]
oxidative
product
[L2Sb2Co(CO)3][OTf]3
[7][OTf]3.
compounds
were
characterized
both
solid
solution
states.
Computational
studies
comprehensive
understanding
experimental
findings.
Язык: Английский
Reactivity Study of the Bis(phosphine)-Stabilized Antimony(I) Cation
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(51), С. 24306 - 24312
Опубликована: Дек. 11, 2024
The
5,6-Bis(diisopropylphosphino)acenaphthene
L-stabilized
Sb(I)
cationic
compound
[LSb][OTf]
(OTf
=
CF3SO3)
1
possessing
two
lone
pairs
of
electrons
on
the
center
showed
nucleophilic
behavior
toward
methyl
trifluoromethanesulfonate
forming
oxidized
product
[LSbMe][OTf]2
2
CF3SO3).
Reaction
with
Lewis
acids
such
as
GaCl3
and
AlBr3
led
to
changes
in
counteranions
only
giving
products
[LSb][GaCl4]
3
[LSb][SbBr4]
4,
respectively.
A
metathesis
reaction
was
observed
when
reacted
PI3.
cation
underwent
P(I)
cation,
more
stable
[LP][OTf]
5.
completely
Sb(V)
by
reacting
equivalents
o-chloranil
give
Bis(phosphine)-stabilized
Bis(perchloro
catecholato)stibonium
[L(O2C6Cl4)2Sb][OTf]
6.
Both
compounds
6
were
employed
proof-of-concept
acid
catalysts
for
hydrosilylation
p-methyl
benzaldehyde.
All
characterized
using
single-crystal
X-ray
diffraction
analysis,
multinuclear
nuclear
magnetic
resonance
spectroscopy,
mass
spectrometry,
absorbance
spectroscopy.
Density
functional
theory
calculations
performed
relevant
compounds.
Язык: Английский