Cooperative Heterobimetallic CO2 Activation Involving a Mononuclear Aluminum(II) Intermediate
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 3, 2025
Molecular
chemistry
of
aluminum
most
commonly
involves
AlIII
ions
due
to
their
noble
gas
electronic
configurations.
In
contrast,
the
AlII
is
underexplored
and
may
contain
undiscovered
reaction
manifolds.
Here,
we
report
CO2
activation
a
transient
intermediate
supported
by
chelating,
dianionic
ligand
investigate
structure
details
mechanisms
required
access
this
reactivity.
We
found
that
heterobinuclear
complex,
(NON)Al-FeCp(CO)2
(1),
undergoes
Al-Fe
bond
homolysis
at
ambient
conditions
reveal
[(NON)Al]•/[CpFe(CO)2]•
radical
pair
in
situ.
The
presence
predominantly
Al-centered
spin
density
(i.e.,
an
ion)
within
was
established
quantum-chemical
calculations
with
experiments
which
scavengers
(TEMPO,
benzophenone)
induce
homolysis.
Exposure
1
atmosphere
resulted
insertion
into
bond.
This
net
2-electron
reduction
process
computationally
modeled
using
functional
theory
direct
dynamics
simulations,
revealing
two
1-electron
steps
and,
thus,
depends
on
stabilization
high-energy
[CO2]•-
coordination
aluminum.
mechanism
for
unexpected
given
canonical
predisposition
multielectron
processes
demonstrates
possibility
discovering
new
profiles
earth-abundant
elements
unusual
oxidation
states.
Language: Английский
Synthesis of Cyclic (Alkyl)(amino)carbene-Stabilized Copper–Iron Heterobimetallic Complexes and Their Application in Pyridine Hydroboration
Organometallics,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 26, 2024
In
this
report,
we
synthesized
heterobimetallic
complexes
supported
by
cyclic
and
bicyclic
(alkyl)(amino)carbenes
(CAAC
EtBICAAC)
[(Me2CAAC)CuFe(η5-C5H5)(CO)2](1)
[(EtBICAAC)CuFe(η5-C5H5)(CO)2]
(2),
respectively,
featuring
an
iron–copper
bond.
Complex
1
demonstrates
catalytic
activity
for
selective
1,4-hydroboration
reactions
of
pyridine
derivatives.
Detailed
computational
studies
provide
additional
insights
into
the
electronic
structure
2
elucidate
pathway.
Language: Английский