Journal of Coordination Chemistry,
Год журнала:
2024,
Номер
unknown, С. 1 - 13
Опубликована: Ноя. 14, 2024
This
study
addresses
the
often-overlooked
chemistry
of
germanium
compared
to
extensively
researched
carbon
and
silicon.
Using
advanced
DFT
methods,
we
investigated
thermal
decomposition
germolane
(germacyclopentane).
The
suggested
mechanisms
include
a
1,2-H
shift
1,1-H2
elimination
form
pentacyclic
germylene
(1λ2-germolane).
other
pathway
involves
stepwise
[3
+
2]
cycloreversion
diradical
followed
by
ethene
germirane.
Under
M062X/def2-TZVP
level
theory,
activation
barriers
in
terms
Gibbs
energy
(ΔG‡298)
for
pathways
were
240.9
236.3
kJ/mol,
respectively.
reaction
energies
(ΔG°298)
initiative
steps
102.9
96.2
indicating
thermodynamic
kinetic
competition
between
two
routes.
Temperature
dependence
analysis
from
300
1200
K
reveals
that
dominates
at
higher
temperatures
is
expected
become
spontaneous
above
1000
K.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(21), С. 14445 - 14452
Опубликована: Май 13, 2024
Transition-metal-catalyzed
C–Si/Ge
cross-coupling
offers
promising
avenues
for
the
synthesis
of
organosilanes/organogermanes,
yet
it
is
fraught
with
long-standing
challenges.
A
Ni/Ti-catalyzed
strategy
reported
here,
allowing
use
disubstituted
malononitriles
as
tertiary
C(sp3)
coupling
partners
to
couple
chlorosilanes
and
chlorogermanes,
respectively.
This
method
enables
catalytic
cleavage
C(sp3)–CN
bond
quaternary
carbon
followed
by
formation
C(sp3)–Si/C(sp3)–Ge
bonds
from
ubiquitously
available
starting
materials.
The
efficiency
generality
are
showcased
a
broad
scope
both
partners,
therefore
holding
potential
synthesize
structurally
diverse
organosilanes
organogermanes
that
were
difficult
access
previously.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(41)
Опубликована: Май 8, 2024
Abstract
We
have
established
a
facile
and
efficient
protocol
for
the
generation
of
germyl
radicals
by
employing
photo‐excited
electron
transfer
(ET)
in
an
donor‐acceptor
(EDA)
complex
to
drive
hydrogen‐atom
(HAT)
from
hydride
(R
3
GeH).
Using
catalytic
amount
EDA
commercially
available
thiol
benzophenone
derivatives,
ET‐HAT
cycle
smoothly
proceeds
simply
upon
blue‐light
irradiation
without
any
transition
metal
or
photocatalyst.
This
also
affords
silyl
radical
hydride.
Chemical Communications,
Год журнала:
2024,
Номер
60(51), С. 6556 - 6559
Опубликована: Янв. 1, 2024
Herein,
a
novel
strategy
is
presented
for
the
photoinduced
decarboxylative
and
dehydrogenative
cross-coupling
of
wide
range
α-fluoroacrylic
acids
with
hydrogermanes.
This
methodology
provides
an
efficient
robust
approach
producing
various
germylated
monofluoroalkenes
excellent
stereoselectivity
within
brief
photoirradiation
period.
The
feasibility
this
reaction
has
been
demonstrated
through
gram-scale
reaction,
conversion
monofluoroalkenes,
modification
complex
organic
molecules.
ACS Catalysis,
Год журнала:
2025,
Номер
15(3), С. 2150 - 2157
Опубликована: Янв. 22, 2025
This
study
reports
the
development
of
a
photocatalytic
germanyl
functionalization
unactivated
olefins.
A
modular
approach
to
alkylgermanium
trihalides
was
realized
through
three-component
radical
reaction
involving
fluoroalkyl
bromides
and
commercially
available
GeBr2
in
redox-neutral
process.
The
target
organogermanes
were
readily
obtained
via
one-pot
derivatization
using
various
Grignard
reagents,
demonstrating
good
functional
group
compatibility
with
amides,
esters
ketones.
work
highlights
utility
Ge(II)
reagents
constructing
C–Ge
bonds
photoredox
catalysis.
Notably,
selectivity
capturing
electrophilic
or
nucleophilic
radicals
by
found
be
significantly
influenced
halide
ligands
on
GeX2.
A
photoredox/nickel
dual
catalytic
system
was
developed
for
the
three-component
1,2-carboalkynylation
of
alkenes.
This
redox-neutral
protocol
enables
efficient
and
divergent
synthesis
aliphatic
alkynes
in
high
yields
with
excellent
regioselectivity,
using
readily
available
starting
materials.
The
resulting
adducts
can
be
transformed
into
terminal
alkynes,
facilitating
diverse
downstream
transformations.
Mechanistic
studies
were
performed
to
elucidate
preferred
pathway
this
alkene
difunctionalization
process.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(14), С. 10004 - 10011
Опубликована: Июнь 27, 2024
-Alkoxyphthalimides,
one
kind
of
phthalimide
derivative,
have
great
importance
in
synthesis,
mainly
used
as
free
radical
precursors.
While
the
unit,
for
a
long
time,
was
treated
part
waste
stream.
Construction
C-N
bonds
has
always
been
hot
spot,
especially
reductive
cross-coupling.
Herein,
nickel-catalyzed
cross-coupling
reaction
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(17), С. 12848 - 12852
Опубликована: Авг. 15, 2024
We
describe
a
visible
light-induced
palladium-catalyzed
radical
germylative
arylation
of
alkenes
with
easily
accessible
chlorogermanes.
This
protocol
provides
expedient
access
to
germanium-substituted
indolin-2-ones
in
good
excellent
yields
under
mild
reaction
conditions.
The
key
step
for
this
strategy
lies
the
reductive
activation
germanium–chloride
bonds
an
excited
palladium
complex
light
irradiation.
involvement
germanium
radicals
was
evidenced
by
electron
paramagnetic
resonance
spectroscopy
experiments.
