Molecules,
Journal Year:
2024,
Volume and Issue:
29(24), P. 5974 - 5974
Published: Dec. 18, 2024
Dihydrogen
activation
by
metallogermylenes
was
investigated
experimentally
and
theoretically.
A
neutral
NHC-coordinated
chlorometallogermylene
synthesized
converted
to
a
cationic
base-free
metallogermylene
of
molybdenum
via
chloride
abstraction.
The
molybdogermylene
showed
enhanced
reactivity
toward
H2
compared
the
tungsten
analog.
reaction
mechanism
theoretical
calculations,
which
revealed
novel
route
that
proceeds
new
type
metal–ligand
cooperative
between
metal
divalent
germanium
moiety.
energy
this
is
much
lower
than
alternative
an
“oxidative
addition”
on
single
Ge(II)
center,
generally
proposed
for
organotetrylenes.
features
frontier
orbitals
origin
effect
are
also
described.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 16, 2025
The
first
bottleable
example
of
a
neutral
Group
13
atom
bound
only
by
donor
ligands
(L)
has
been
fully
characterized
spectroscopic
methods
and
its
structure
determined
single-crystal
X-ray
diffraction
study.
A
two-coordinate
paramagnetic
L2B0
complex
can
readily
be
accessed
through
facile
reduction
reaction
is
stabilized
π-accepting
cyclic
(alkyl)(amino)carbene
(CAAC)
ligands.
Further
(CAAC)2B
leads
to
the
isolation
stable
diamagnetic
boride
anion.
In
turn,
oxidation
putative
formation
transient
cationic
borylene,
which
trapped
form
boron(I)
complex.
Density
functional
theory
calculations
support
formulation
as
boron(0)
strong
multiple
bonding.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
The
di-NHCs-stabilized
stannyliumylidene
serves
as
an
efficient
pre-catalyst
for
the
selective
hydrosilylation
of
CO
2
to
silyl
formate.
Experimental
mechanistic
studies
and
quantum
chemical
calculations
revealed
mechanism.
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.
The
pursuit
of
practical,
straightforward,
and
sustainable
methods
for
forming
carbon-phosphorus
bonds
is
crucial
in
both
academia
industry.
Traditional
synthetic
often
rely
on
hazardous,
halogenated
precursors
through
salt-metathesis
routes.
In
this
study,
we
have
synthesized
characterized
magnesium
complexes
[L(Mg-nBu)2]
(L
=
bis(diiminate);
nBu
n-butyl)
1
2.
Complex
effectively
catalyzes
the
hydrophosphinylation
alkynes
resulting
stepwise
hydrophosphinylated
products
namely
monophosphinylated
vinyledene-
1,2-diphosphinylated
alkanes.
While
doubly
addition
with
are
predominant,
catalytic
reaction
produces
anti-Markovnikov
inactivated
alkenes,
whereas
activated
alkenes
giving
rise
to
conjugated
products.
This
transformation
showcases
an
excellent
atom
economy,
broad
functional
group
tolerance
gram
scale
synthesis
organophosphorus
compounds.
Through
controlled
experiments,
kinetic
studies,
density
theoretical
calculations,
elucidated
mechanism,
identifying
active
species
revealing
a
process
alkynes.
Although
complex
showed
its
potential
alkynes,
2
3
produced
lower
yield
products,
indicating
role
ligand
(spacer)
transformation.
work
first
demonstrate
that
neutral
can
independently
catalyse
offers
opportunities
other
compounds
catalyzed
by
main-group
metal
complexes.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(73), P. 9958 - 9961
Published: Jan. 1, 2024
Herein,
we
report
a
hybrid
silylene-based
bidentate
ligand
(SiNP)–Pd(0)
catalytic
system,
which
performs
the
C–N
coupling
of
difficult
substrates,
e.g
.,
sterically
bulky
amines
and
chiral
amines.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 10, 2024
Abstract
Aromatic
substitution
of
redox‐active
aromatic
compounds
could
be
initiated
by
a
preceding
redox
step.
We
report
on
the
different
reaction
pathways
such
redox‐induced
(RIAS)
reactions
between
guanidino‐functionalized
molecule
(GFA)
and
an
amine
or
guanidine.
Oxidation
GFA
leads
to
umpolung
guanidine
from
nucleophile
electrophile
thereby
enables
addition
Several
examples
are
given,
demonstrating
use
in
synthetic
chemistry,
e.
g.
for
convenient
synthesis
novel
N
‐heteropolycyclic
molecules
unsymmetrically‐substituted
aromatics.
