Macromolecules,
Journal Year:
2024,
Volume and Issue:
57(10), P. 4926 - 4936
Published: May 15, 2024
Ester
and
amide
enolates
are
important
propagating
species
in
organometallic-mediated
polymerization
of
polar
vinyl
monomers,
but
the
effects
transition
main
group
metallic
counterions
have
not
been
systematically
understood.
In
this
study,
various
metal
triflates
along
with
PPh3
used
to
catalyze
Lewis
pair
anionic
(LPAP)
or
radical
(LPRP)
(meth)acrylates
acrylamides,
elements
solvents
determine
dominant
propagation
mechanism.
Specifically,
LPAP
LPRP
proceed
using
early
late
triflates,
respectively,
organic
on-water.
The
elementary
reactions
PPh3/Fe(OTf)3
kinetically
investigated.
Notably,
follows
pseudo-second-order
kinetics
respect
monomer
concentration,
which
contributes
initiation
propagation,
whereas
PPh3/Sc(OTf)3
proceeds
pseudo-zero-order
kinetics.
This
indicates
that
react
unactivated
free
Sc-activated
LPAP.
study
demonstrates
triflate-based
pairs
can
generate
new
polymerizable
distinctive
reactivities.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 8, 2024
Although
diradicals
should
exhibit
a
rather
small
reaction
barrier
as
compared
to
closed-shell
species
for
activating
kinetically
inert
molecules,
the
activation
and
functionalization
of
carbon
dioxide
with
stable
main-group
remain
virtually
unexplored.
In
this
work,
we
present
thorough
study
on
CO2
activation,
reversible
capture,
(de)oxygenation
mediated
by
Group
14
singlet
(i.e.,
diradicaloids)
[(ADC)E]2
(E
=
Si,
Ge,
Sn)
based
an
anionic
dicarbene
(ADC)
framework
(ADC
PhC{N(Dipp)C}2;
Dipp
2,6-iPr2C6H3).
readily
undergo
[4
+
2]-cycloadditions
result
in
barrelene-type
bis-metallylenes
[(ADC)E]2(OC═O).
The
addition
is
E
Ge;
thus,
detaches
under
vacuum
or
at
elevated
temperature
regenerates
[(ADC)Ge]2.
[(ADC)Sn]2(OC═O)
isolable
but
deoxygenates
additional
form
[(ADC)Sn]2(O2CO)
CO.
[(ADC)Si]2(OC═O)
extremely
reactive
could
not
be
isolated
detected
it
spontaneously
reacts
further
yield
elusive
monomeric
Si(IV)
oxides
[(ADC)Si(O)]2(COn)
carbonates
[(ADC)Si(CO3)]2(COn)
(n
1
2)
via
CO2.
molecular
structures
all
compounds
have
been
established
X-ray
diffraction,
mechanistic
insight
their
formation
has
suggested
DFT
calculations.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(19)
Published: March 5, 2024
Abstract
We
have
synthesized
a
quinone‐incorporated
bistriarylamine
donor‐acceptor‐donor
(D–A–D)
semiconductor
1
by
B(C
6
F
5
)
3
(BCF)
catalyzed
C−H/C−H
cross
coupling
via
radical
ion
pair
intermediates.
Coordination
of
Lewis
acids
BCF
and
Al(OR
(R
=C(CF
to
the
afforded
diradical
zwitterions
2
integer
electron
transfer.
Upon
binding
acids,
LUMO
energy
is
significantly
lowered
band
gap
narrowed
from
1.93
eV
(
1.01
1.06
).
are
rare
near‐infrared
(NIR)
dyes
with
broad
absorption
both
centered
around
1500
nm.
By
introducing
photo
generator,
can
be
generated
light‐dependent
control.
Furthermore,
transfer
process
also
reversibly
regulated
addition
CH
CN.
In
addition,
temperature
sharply
increased
reached
as
high
110
°C
in
10
s
upon
irradiation
near‐infrared‐II
(NIR‐II)
laser
(1064
nm,
0.7
W
cm
−2
),
exhibiting
fast
response
laser.
It
displays
excellent
photothermal
stability
(PT)
conversion
efficiency
62.26
%
high‐quality
PT
imaging.
Macromolecules,
Journal Year:
2024,
Volume and Issue:
57(10), P. 4926 - 4936
Published: May 15, 2024
Ester
and
amide
enolates
are
important
propagating
species
in
organometallic-mediated
polymerization
of
polar
vinyl
monomers,
but
the
effects
transition
main
group
metallic
counterions
have
not
been
systematically
understood.
In
this
study,
various
metal
triflates
along
with
PPh3
used
to
catalyze
Lewis
pair
anionic
(LPAP)
or
radical
(LPRP)
(meth)acrylates
acrylamides,
elements
solvents
determine
dominant
propagation
mechanism.
Specifically,
LPAP
LPRP
proceed
using
early
late
triflates,
respectively,
organic
on-water.
The
elementary
reactions
PPh3/Fe(OTf)3
kinetically
investigated.
Notably,
follows
pseudo-second-order
kinetics
respect
monomer
concentration,
which
contributes
initiation
propagation,
whereas
PPh3/Sc(OTf)3
proceeds
pseudo-zero-order
kinetics.
This
indicates
that
react
unactivated
free
Sc-activated
LPAP.
study
demonstrates
triflate-based
pairs
can
generate
new
polymerizable
distinctive
reactivities.
