Chemical Communications,
Год журнала:
2024,
Номер
60(69), С. 9222 - 9225
Опубликована: Янв. 1, 2024
Boraadamantanes
are
a
privileged
class
of
caged
group
13
compounds
having
trigonal
pyramidal
(non-VSEPR)
ground-state.
The
Lewis
acid-base
chemistry
this
type
compound
is
underdeveloped
when
compared
to
acyclic
derivatives.
This
report
provides
the
first
examples
bifunctional
boraadamantanes
with
an
appended
phosphine
moiety
(also
phosphorus-boron
bond).
Using
scaffold,
boraadamantane
coordination
accessed
for
time.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Апрель 10, 2024
The
reduction
of
dioxygen
to
water
is
crucial
in
biology
and
energy
technologies,
but
it
challenging
due
the
inertness
triplet
oxygen
complex
mechanisms.
Nature
leverages
high-spin
transition
metal
complexes
for
this,
whereas
main-group
compounds
with
their
singlet
state
limited
redox
capabilities
exhibit
subdued
reactivity.
We
present
a
novel
phosphorus
capable
four-electron
reduction,
facilitated
by
unique
phosphorus-ligand
cooperativity.
Spectroscopic
computational
investigations
attribute
this
cooperative
reactivity
electronic
structure
arising
from
geometry
bestowed
ligand.
Mechanistic
study
via
spectroscopic
kinetic
experiments
revealed
involvement
elusive
intermediates
resembling
those
metalloenzymes.
Our
result
highlights
multielectron
compound
emerging
carefully
designed
ligand
platform
anticipate
that
work
described
expands
strategies
developing
catalytic
reactions,
especially
small
molecule
fixations
demanding
processes.
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Май 23, 2024
Abstract
Silyl
anions
have
garnered
significant
attention
due
to
their
synthetic
abilities.
However,
previously
reported
silyl
been
limited
either
trigonal‐pyramidal
or
trigonal‐planar
geometries,
which
confine
them
primarily
as
nucleophiles
in
substitution
reactions.
Herein,
we
report
the
isolation
of
unprecedented
T‐shaped
planar
anion
salt
2
by
employment
a
geometrically
constrained
triamido
pincer
ligand.
Theoretical
calculations
disclosed
that
silicon
centre
possesses
both
lone
pair
electrons
and
an
empty
3p
z
orbital.
In
addition
nucleophilic
reactions
with
Ph
3
PAuCl
W(CO)
6
,
readily
undergoes
oxidative
additions
CO
2,6‐dimethylphenylisonitrile
at
room
temperature.
Furthermore,
under
mild
conditions,
compound
cleaves
C
sp2
−H,
H−H
bonds
1,2,4,5‐tetrafluorobenzene,
intramolecular
i
Pr
group,
dihydrogen,
representing
first
examples
C−H
activations
mediated
anion,
respectively.
This
work
unveils
new
reactivity
owing
non‐classical
geometry
electronic
structure.
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(32), С. 14969 - 14980
Опубликована: Июль 29, 2024
While
metal-ligand
cooperativity
is
well-known,
studies
on
element-ligand
involving
main
group
species
are
comparatively
much
less
explored.
In
this
study,
we
computationally
designed
a
few
geometrically
constrained
borylenes
supported
by
different
carbenes.
Our
density
functional
theory
indicate
that
they
possess
enhanced
nucleophilicity
as
well
electrophilicity,
thus
rendering
them
promising
candidates
for
exhibiting
borylene-ligand
cooperativity.
The
cooperation
between
the
boron
and
adjacent
carbene
centers
facilitates
bond
activation
processes,
including
cycloaddition
of
acetylene
across
boron-carbene
B-H/Si-H
reactions,
which
have
been
analyzed
in
detail.
To
best
our
knowledge,
proposed
study
represent
first
examples
theoretically
bis(carbene)-stabilized
capable
cooperative
enthalpically
strong
bonds.
Chemical Communications,
Год журнала:
2024,
Номер
60(69), С. 9222 - 9225
Опубликована: Янв. 1, 2024
Boraadamantanes
are
a
privileged
class
of
caged
group
13
compounds
having
trigonal
pyramidal
(non-VSEPR)
ground-state.
The
Lewis
acid-base
chemistry
this
type
compound
is
underdeveloped
when
compared
to
acyclic
derivatives.
This
report
provides
the
first
examples
bifunctional
boraadamantanes
with
an
appended
phosphine
moiety
(also
phosphorus-boron
bond).
Using
scaffold,
boraadamantane
coordination
accessed
for
time.
