Rhodium(III)‐NSi Catalyzed Styrene Hydrosilylation: Evidence of the Hemilabile Character of NSi‐type Ligands
Chemistry - A European Journal,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 21, 2025
The
18e
saturated
rhodium(III)
species
[Rh(H)(X)(κ2-NSitBu2)(bipyMe2)]
(NSitBu2={4-methylpyridine-2-yloxy}ditertbutylsilyl;
bipyMe2=4,4'-dimethylbipyridine)
(X=Cl,
1;
OTf,
2)
have
been
prepared
and
characterized
by
NMR
spectroscopy
in
the
case
of
2
it
has
possible
to
determine
its
solid-state
structure
X-ray
diffraction.
Complex
1
proven
be
an
effective
catalyst
precursor
for
reaction
styrene
derivatives
with
hydrosilanes
CD2Cl2.
However,
under
catalytic
conditions
complex
decomposes.
performance
1-catalyzed
strongly
depends
on
nature
silane,
best
was
achieved
using
HSiMe2Ph.
Theoretical
1H
studies
indicate
that
hemilabile
NSi
ligand
is
key
understanding
activity
compound
1.
Язык: Английский
Catalytic Asymmetric Dehydrogenative Si–H/X–H Coupling toward Si-Stereogenic Silanes
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 22, 2025
ConspectusChiral
organosilicon
compounds
bearing
a
Si-stereogenic
center
have
attracted
increasing
attention
in
various
scientific
communities
and
appear
to
be
topic
of
high
current
relevance
modern
organic
chemistry,
given
their
versatile
utility
as
chiral
building
blocks,
reagents,
auxiliaries,
catalysts.
Historically,
access
these
non-natural
silanes
mainly
relies
on
resolution,
whereas
asymmetric
synthetic
methods
dramatically
lagged
compared
carbon
counterparts.
Over
the
past
two
decades,
transition-metal-catalyzed
desymmetrization
prochiral
organosilanes
has
emerged
an
effective
tool
for
synthesis
enantioenriched
silanes.
Despite
progress,
catalytic
reactions
usually
suffer
from
limited
substrate
scope,
poor
functional-group
tolerance,
low
enantioselectivity.
The
growing
demand
with
structural
diversity
continued
drive
development
new
practical
assembly
molecules.Five
years
ago,
our
research
group
embarked
project
aimed
at
developing
general
approach
that
can
unlock
functionalized
efficiency.
This
Account
describes
laboratory's
endeavor
exploration
dehydrogenative
Si–H/X–H
coupling
toward
features
(1)
readily
accessible
dihydrosilane
starting
materials;
(2)
diverse
X–H
(X═C,
N,
O,
etc.)
partners;
(3)
platform
transformable
monohydrosilane
products;
(4)
efficiency
atomic
economy.At
initial
stage
research,
biaryl
was
selected
model
conduct
enantioselective
intramolecular
C–H/Si–H
reaction.
Rh/Josiphos
system
found
early
this
process,
while
final
enantiocontrol
elusive.
Mechanistic
studies
indicated
rhodium
silyl
dihydride
complex
is
resting
state
cycle,
which
may
undergo
racemization
center.
Enlightened
by
mechanistic
investigations,
strategies,
tandem
alkene
hydrosilylation
strategy
bulky
alkene-assisted
strategy,
were
adopted
avoid
racemization,
delivering
corresponding
9-silafluorenes
excellent
yields
enantioselectivities.
Further
C(sp2)–H
or
C(sp3)–H
silylation
gave
series
five-,
six-
seven-membered
heterocycles
Next,
we
extended
reaction
intermolecular
version,
realizing
Si–H/C–H,
Si–H/O–H,
Si–H/N–H
variety
acyclic
monohydrosilanes,
ethers,
siloxanes,
silanols,
silazanes.
We
also
presented
endeavors
apply
resulting
compounds,
including
further
derivatization,
polymerization,
chiroptical
property
successfully
introduced
Si-stereocenters
into
bioactive
molecules,
polymers,
materials.
Lastly,
based
understanding
metal
species,
developed
type
ligand
applied
enable
atroposelective
anticipate
methodology,
insights,
studies,
will
not
only
inspire
chemistry
but
contribute
creation
novel
molecules
medicinal
materials
science.
Язык: Английский
X-Type Silyl Ligands Mediated C—H Functionalization Reactions
Chinese Journal of Organic Chemistry,
Год журнала:
2025,
Номер
45(2), С. 641 - 641
Опубликована: Янв. 1, 2025
Язык: Английский
Catalytic acceptorless dehydrogenation of alcohols using cobalt(i) pincer complexes supported by a P–GeH–P ligand
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
We
report
a
novel
P–GeH–P
pincer
ligand
and
its
cobalt(
i
)
complex,
which
catalyzes
the
acceptorless
dehydrogenation
of
alcohols.
Язык: Английский
Recent Advances on the Chemistry of Transition Metal Complexes with Monoanionic Bidentate Silyl Ligands
ChemPlusChem,
Год журнала:
2024,
Номер
unknown
Опубликована: Май 23, 2024
The
chemistry
of
transition-metal
(TM)
complexes
with
monoanionic
bidentate
(κ
Язык: Английский
Coordination chemistry of ligands bearing heavy group 14 and 15 elements: Comparative analysis of their influence on transition metal chemistry
Coordination Chemistry Reviews,
Год журнала:
2024,
Номер
526, С. 216317 - 216317
Опубликована: Дек. 3, 2024
Язык: Английский
Cross-Dehydrogenative Coupling of Secondary Amines with Silanes Catalyzed by Agostic Iridium-NSi Species
Inorganic Chemistry,
Год журнала:
2024,
Номер
64(1), С. 255 - 267
Опубликована: Дек. 23, 2024
An
active
catalytic
system
for
the
cross-dehydrogenative
coupling
(CDC)
of
a
wide
range
secondary
amines
with
silanes
is
reported.
The
iridium(III)
derivatives
[Ir(H)(X)(κ2-NSiDMQ)(L)]
(NSiDMQ
=
{4,8-dimethylquinoline-2-yloxy}dimethylsilyl;
L
coe,
X
Cl,
2;
OTf,
3;
PCy3,
4;
5),
which
are
stabilized
by
weak
yet
noticeable
Ir···H–C
agostic
interaction
between
iridium
and
one
C–H
bonds
8-Me
substituent
NSiDMQ
ligand,
have
been
prepared
fully
characterized.
These
species
proven
to
be
effective
catalysts
CDC
hydrosilanes.
best
performance
(TOF1/2
79,300
h–1)
was
obtained
using
5
(0.25
mol
%),
N-methylaniline,
HSiMe2Ph.
activity
[Ir(H)(OTf)(κ2-NSiQ)(PCy3)]
(10,
NSiQ
{quinoline-2-yloxy}dimethylsilyl)
[Ir(H)(OTf)(κ2-NSiMQ)(PCy3)]
(11,
NSiMQ
{4-methylquinoline-2-yloxy}dimethylsilyl),
related
but
lacking
substituent,
markedly
lower
than
that
found
5.
This
fact
highlights
crucial
role
ligand
in
enhancing
these
complexes.
Язык: Английский
Forging of silaoxycarbocyclics by interrupted Catellani reaction
Chinese Chemical Letters,
Год журнала:
2024,
Номер
unknown, С. 110474 - 110474
Опубликована: Сен. 1, 2024
Язык: Английский
Theoretical study of the structure and stability of silyl cations with lewis bases using DFT and NBO analysis
STUDIES IN ENGINEERING AND EXACT SCIENCES,
Год журнала:
2024,
Номер
5(3), С. e12703 - e12703
Опубликована: Дек. 26, 2024
This
study
investigates
the
intricate
interplay
between
electronic
and
steric
factors
in
shaping
Si-P
bond
lengths,
angles,
binding
energies,
charge
distribution,
interaction
energies
silicon-centered
cation-phosphine
base
systems.
A
detailed
analysis
reveals
that
(CH₃)₃Si⁺
exhibits
shortest
lengths
(2.01–2.03
Å),
attributed
to
minimal
hindrance
favorable
overlap.
In
contrast,
(C₂H₅)₃Si⁺
displays
slightly
longer
(2.03–2.05
while
longest
are
observed
Ar₃Si⁺
(2.08–2.10
due
combined
electron-withdrawing
nature
effects
of
aromatic
groups.
Variations
angles
further
demonstrate
influence
bulk
effects,
with
(C₂H₅)₃P
consistently
exhibiting
larger
(e.g.,
120°–121°
for
Ar₃Si⁺)
compared
(CH₃)₃P.
Binding
energy
calculations
identify
most
(-28
kcal/mol)
(CH₃)₃P,
driven
by
an
optimal
balance
geometry
distribution.
Charge
transfer
indicates
donates
more
electron
density
than
consistent
trends
expected
from
considerations.
Natural
Bond
Orbital
(NBO)
confirms
a
strong
negative
correlation
σ-donation
energy,
increased
leading
stronger
interaction,
which
negative.
weaker
interactions
its
These
findings
underscore
critical
role
defining
strengths,
providing
valuable
insights
designing
tailored
silicon-phosphine
complexes
potential
applications
catalysis
material
sciences.
Язык: Английский
Complejos con ligandos sililo polidentados como catalizadores homogéneos en reacciones de hidrogenación e hidrosililación
Deleted Journal,
Год журнала:
2024,
Номер
120(4), С. 192 - 192
Опубликована: Дек. 26, 2024
La
química
de
los
complejos
metales
transición
con
ligandos
monoaniónicos
bidentados
k2-Si,L
y/o
tridentados
k3-Si,L2—donde
Si
simboliza
un
grupo
sililo
y
L
grupos
neutros
dadores
s
par
electrones—ha
despertado
interés
creciente
en
últimos
años.
Esta
revisión
presenta
principales
avances
logrados
la
aplicación
estos
como
catalizadores
procesos
clave,
son
hidrogenación
hidrosililación
moléculas
insaturadas.