Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 8, 2024
Abstract
The
recent
discovery
of
frustrated
Lewis
pairs
(FLPs)
during
the
activation
small
molecules
has
inspired
extensive
research
across
full
span
chemical
science.
Owing
to
nature
weak
interactions,
it
is
experimentally
challenging
directly
observe
and
modulate
FLP
at
molecular
scale.
Here
we
design
a
boron
cluster
anion
building
block
(B
10
H
8
2−
)
organic
amine
cations
([NR
4
]
+
,
R=−CH
3
−C
2
5
as
prove
feasibility
controlling
their
interaction
in
electric
double
layer
(EDL)
via
an
electrochemical
strategy.
In
situ
single‐molecule
electrical
measurements
Raman
monitoring
B
−[NR
formed
positively
charged
Au(111)
electrode
surface,
contrast
free‐standing
near
or
below
potential
zero
charge
(PZC).
Furthermore,
this
chemistry
leads
shift
local
density
states
clusters
towards
E
F
for
enhancing
electron
transport,
providing
new
prototype
reversible
single‐cluster
switch
that
digitally
switches
upon
layer.
Dalton Transactions,
Journal Year:
2023,
Volume and Issue:
53(3), P. 1178 - 1189
Published: Nov. 30, 2023
Coordination
chemistry
and
frustrated
Lewis
pair
(FLP)
have
been
most
commonly
studied
using
monodentate
acids.
In
this
paper,
we
examine
the
corresponding
reactions
employing
1,1-
1,2-bis-boranes,
PhCH
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(48)
Published: Oct. 13, 2023
Abstract
Herein,
we
present
the
formation
of
transient
radical
ion
pairs
(RIPs)
by
single‐electron
transfer
(SET)
in
phosphine−quinone
systems
and
explore
their
potential
for
activation
C−H
bonds.
PMes
3
(Mes=2,4,6‐Me
C
6
H
2
)
reacts
with
DDQ
(2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone)
P−O
bonded
zwitterionic
adduct
Mes
P−DDQ
(
1
),
while
reaction
sterically
more
crowded
PTip
(Tip=2,4,6‐
i
Pr
afforded
bond
product
Tip
P(H)(2‐[CMe
(DDQ)]‐4,6‐
‐C
).
UV/Vis
EPR
spectroscopic
studies
showed
that
latter
proceeds
via
initial
SET,
forming
RIP
[PTip
]⋅
+
[DDQ]⋅
−
,
subsequent
homolytic
activation,
which
was
supported
DFT
calculations.
The
isolation
analogous
products,
{TCQ−B(C
F
5
}]‐4,6‐
4
TCQ=tetrachloro‐1,4‐benzoquinone)
{
o
Q
t
Bu
−B(C
8
=3,5‐di‐
tert
‐butyl‐1,2‐benzoquinone),
from
reactions
Lewis‐acid
activated
quinones,
TCQ−B(C
respectively,
further
supports
proposed
mechanism.
As
such,
this
study
presents
key
mechanistic
insights
into
synergistic
action
pairs.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 23, 2024
Exploration
of
new
heterobinuclear
Al/M
combinations
is
relevant
to
contemporary
strategies
for
cooperative
bond
activation.
Here,
we
report
the
synthesis
and
characterization
six
heterobimetallic
complexes
(M
=
Cr,
Mo,
W)
that
exhibit
end-on
"isocarbonyl"-type
Al─O═C═M
bridges
with
metalloketene
character
rather
than
featuring
Al─M─C≡O
motifs
metal-metal
bonding.
The
compounds
were
characterized
experimentally
by
nuclear
magnetic
resonance
infrared
spectroscopies
theoretically
using
density
functional
theory,
natural
orbital,
quantum
theory
atoms
in
molecules
calculations.
Factors
influencing
vs
isomerism
probed
both
computationally.
Crossover
experiments
between
different
group
VI
derivatives
regioselective
epoxide
ring
opening
indicate
act
as
masked
frustrated
Lewis
pairs
solution
under
certain
conditions.
However,
crossover
a
previously
studied
Al-Fe
complex,
well
computational
modeling,
imply
same
can
also
reasonably
radical
(FRPs).
FRP
reactivity
was
achieved
photochemical
conditions,
producing
unsaturated
metal-carbonyl
dimers
[(CpCr)
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 8, 2024
The
recent
discovery
of
frustrated
Lewis
pairs
(FLPs)
during
the
activation
small
molecules
has
inspired
extensive
research
across
full
span
chemical
science.
Owing
to
nature
weak
interactions,
it
is
experimentally
challenging
directly
observe
and
modulate
FLP
at
molecular
scale.
Here
we
design
a
boron
cluster
anion
building
block
(B
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 8, 2024
Abstract
The
recent
discovery
of
frustrated
Lewis
pairs
(FLPs)
during
the
activation
small
molecules
has
inspired
extensive
research
across
full
span
chemical
science.
Owing
to
nature
weak
interactions,
it
is
experimentally
challenging
directly
observe
and
modulate
FLP
at
molecular
scale.
Here
we
design
a
boron
cluster
anion
building
block
(B
10
H
8
2−
)
organic
amine
cations
([NR
4
]
+
,
R=−CH
3
−C
2
5
as
prove
feasibility
controlling
their
interaction
in
electric
double
layer
(EDL)
via
an
electrochemical
strategy.
In
situ
single‐molecule
electrical
measurements
Raman
monitoring
B
−[NR
formed
positively
charged
Au(111)
electrode
surface,
contrast
free‐standing
near
or
below
potential
zero
charge
(PZC).
Furthermore,
this
chemistry
leads
shift
local
density
states
clusters
towards
E
F
for
enhancing
electron
transport,
providing
new
prototype
reversible
single‐cluster
switch
that
digitally
switches
upon
layer.
