Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(37), P. 14828 - 14832
Published: Sept. 7, 2023
We
demonstrate
the
increased
Lewis
acidity
on
going
from
Sn(II)
to
Sn(IV)
by
oxidizing
TpMe2SnOTf
(OTf
=
SO3CF3)
TpMe2SnF(OTf)2.
Replacement
of
fluoride
ion
in
TpMe2SnF(OTf)2
a
triflate,
resulting
TpMe2Sn(OTf)3
further
enhances
at
tin.
119Sn
NMR
spectroscopy,
modified
Gutmann-Beckett
test,
computational
analysis,
and
catalytic
phosphine
oxide
deoxygenation
support
claims.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
61(4)
Published: Nov. 10, 2021
IUPAC
defines
Lewis
acidity
as
the
thermodynamic
tendency
for
pair
formation.
This
strength
property
was
recently
specified
global
(gLA),
and
is
gauged
example
by
fluoride
ion
affinity.
Experimentally,
usually
evaluated
effect
on
a
bound
molecule,
such
induced
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(24)
Published: Feb. 27, 2023
Key
challenges
in
modern
synthetic
chemistry
include
the
design
of
reliable,
selective,
and
more
sustainable
methods,
as
well
development
promising
candidates
for
new
materials.
Molecular
bismuth
compounds
offer
valuable
opportunities
they
show
an
intriguing
spectrum
properties
that
is
yet
to
be
fully
exploited:
a
soft
character,
rich
coordination
chemistry,
availability
broad
variety
oxidation
states
(at
least
+V
-I)
formal
charges
+3
-3)
at
Bi
atoms,
reversible
switching
between
multiple
states.
All
this
paired
with
status
non-precious
(semi-)metal
good
tendency
towards
low
toxicity.
Recent
findings
some
these
only
come
into
reach,
or
can
substantially
optimized,
when
charged
are
specifically
addressed.
In
review,
essential
contributions
synthesis,
analyses,
utilization
ionic
highlighted.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(36), P. 19458 - 19477
Published: Aug. 30, 2023
Motivated
by
the
discovery
of
main
group
Lewis
acids
that
could
compete
or
possibly
outperform
ubiquitous
organoboranes,
several
groups,
including
ours,
have
engaged
in
chemistry
acidic
organoantimony
compounds
as
new
platforms
for
anion
capture,
sensing,
and
transport.
Principal
to
this
approach
are
intrinsically
elevated
properties
antimony,
which
greatly
favor
addition
halide
anions
15
element.
The
introduction
organic
substituents
antimony
center
its
oxidation
from
+
III
V
state
provide
tunable
acidity
a
breadth
applications
supramolecular
catalysis.
performances
these
antimony-based
domain
sensing
aqueous
media
illustrate
favorable
attributes
central
At
same
time,
recent
advances
binding
catalysis
transport
across
phospholipid
membranes
speak
numerous
opportunities
lie
ahead
unique
compounds.
Inorganic Chemistry,
Journal Year:
2022,
Volume and Issue:
61(46), P. 18640 - 18652
Published: Nov. 9, 2022
We
report
a
comprehensive
assessment
of
Lewis
acidity
for
series
carbone-stibenium
and
-bismuthenium
ions
using
the
Gutmann-Beckett
(GB)
method.
These
new
antimony
bismuth
cations
have
been
synthesized
by
halide
abstractions
from
(CDC)PnBr3
[(pyCDC)PnBr2][Br]
(CDC
=
carbodicarbene;
Pn
Sb
or
Bi;
py
pyridyl).
The
reaction
(CDC)SbBr3
(1)
with
one
two
equivalents
AgNTf2
(NTf2
bis(trifluoromethanesulfonyl)imide)
AgSbF6
gives
stibaalkene
mono-
dications
form
[(CDC)SbBr3-n][A]n
(2-4;
n
1,2;
A
NTf2
SbF6).
trication
[(CDC)2Sb][NTf2]3
(5)
was
also
isolated
collectively
these
molecules
fill
gap
among
cationic
pnictaalkenes.
are
compared
to
related
CDC-bismaalkene
complexes
6-9.
With
goal
preparing
highly
acidic
compounds,
tridentate
bis(pyridine)carbodicarbene
(pyCDC)
used
as
ligand
access
(10,
12)
trications
[(pyCDC)Pn][NTf2]3
(Pn
(11),
Bi
(13)),
forgoing
need
second
CDC
in
synthesis
5.
bonding
situation
is
elucidated
through
electron
density
energy
decomposition
analyses
combination
natural
orbital
chemical
valence
theory.
In
each
complex,
there
exists
CDC-Pn
double
interaction,
consisting
strong
σ-bond
weaker
π-bond,
whereby
π-bond
gradually
strengthens
increase
charge
complex.
Notably,
[(CDC)SbBr][NTf2]2
(4)
has
an
acceptor
number
(AN)
(84)
that
comparable
quintessential
acids
such
BF3,
tricationic
pnictaalkene
11
13
exhibit
ANs
109
Sb)
84
Bi),
respectively,
which
highest
values
reported
any
cation.
Moreover,
calculated
fluoride
ion
affinities
(FIAs)
99.8
94.3
kcal/mol,
larger
than
SbF5
(85.1
kcal/mol),
suggest
superacids.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(46)
Published: Sept. 29, 2023
Abstract
A
bidentate
pnictogen
bonding
host‐system
based
on
1,8‐diethynylanthracene
was
synthesized
by
a
selective
tin‐antimony
exchange
reaction
and
investigated
regarding
its
ability
to
act
as
Lewis
acidic
host
component
for
the
complexation
of
basic
or
anionic
guests.
In
this
work,
novel
C≡C−Sb(C
2
F
5
)
unit
established
study
potential
antimony(III)
sites
representatives
scarcely
explored
donors.
The
capability
partly
fluorinated
system
towards
halide
anions
(Cl
−
,
Br
I
),
dimethyl
chalcogenides
Me
Y
(Y=O,
S,
Se,
Te),
nitrogen
heterocycles
(pyridine,
pyrimidine).
Insights
into
adduct
formation
behavior
well
situation
such
E⋅⋅⋅Sb−C
moieties
were
obtained
in
solution
means
NMR
spectroscopy,
solid
state
X‐ray
diffraction,
elemental
analyses,
computational
methods
(DFT,
QTAIM,
IQA),
respectively.
Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(11), P. 4590 - 4597
Published: March 3, 2023
Organobismuth
compounds
have
been
studied
in
various
fields,
including
electronic
states,
pnictogen
bonds,
and
catalysis.
Among
them,
one
of
the
unique
states
element
is
hypervalent
state.
So
far,
many
issues
regarding
structures
bismuth
revealed;
meanwhile,
influence
on
properties
π-conjugated
scaffolds
still
vailed.
Here,
we
synthesized
compound,
BiAz,
by
introducing
into
azobenzene
tridentate
ligand
as
a
scaffold.
The
was
evaluated
from
optical
measurements
quantum
chemical
calculations.
introduction
revealed
three
significant
effects:
first,
shows
position-dependent
electron-donating
electron-accepting
effects.
Second,
BiAz
can
larger
effective
Lewis
acidity
than
tin
compound
derivatives
reported
our
previous
research.
Finally,
coordination
dimethyl
sulfoxide
transformed
similar
to
compounds.
data
calculations
showed
that
scaffold
were
able
be
changed
bismuth.
To
best
knowledge,
first
demonstrate
should
new
methodology
for
controlling
molecules
developing
sensing
materials.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(6), P. 3909 - 3915
Published: March 1, 2023
A
novel
method
for
the
iodine-mediated
reduction
of
phosphine
oxides
(sulfides)
to
phosphines
using
phosphonic
acid
under
solvent-free
conditions
is
described.
By
a
combination
H3PO3
and
I2,
both
tertiary
monophosphine
bis-phosphine
were
reduced
this
system,
readily
producing
monodentate
bidentate
phosphines,
respectively,
in
good
yields.
Notably,
chiral
(R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl
dioxide
could
be
also
tolerated
without
racemization.
This
new
approach
inexpensive
features
simple
wide
substrate
scope.
Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(33), P. 13566 - 13572
Published: Aug. 8, 2023
We
report
the
results
of
a
computational
investigation
into
fluoride
binding
by
series
pentavalent
pnictogen
Lewis
acids:
pentahalides
(PnX5),
tetraphenyl
pnictogeniums
(PnPh4+),
and
triphenyl
tetrachlorocatecholates
(PnPh3Cat).
Activation
strain
energy
decomposition
analyses
adducts
not
only
clearly
delineate
electrostatic
orbital
contributions
to
these
acid–base
interactions
but
also
highlight
importance
Pauli
repulsion
molecular
flexibility
in
determining
relative
acidity
among
pnictogens.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(30), P. 12118 - 12125
Published: Jan. 1, 2024
(F
5
C
2
)
SbCH
P(
t
Bu)
reacts
in
a
FLP-like
manner
with
CS
,
SO
PhNCO/S
and
(MePh
P)AuCl.
The
AuCl
adduct
show
secondary
interactions
between
the
Lewis
acidic
Sb
atom
electron
rich
atoms,
intra-
intermolecular,
respectively.
