Chemical Communications,
Год журнала:
2023,
Номер
59(67), С. 10117 - 10120
Опубликована: Янв. 1, 2023
A
systematic
study
on
the
reactivity
of
cyclo-P4
complexes
[CpRTa(CO)2(η4-P4)]
towards
pnictogenium
cations
results
in
formation
functionalised
interpnictogen
cations.
Phosphenium
ions
insert
into
one
P-P
bonds
to
give
ring-expanded
cyclo-P5R2
products.
In
contrast,
an
arsenium-functionalised
P4AsCy2
ligand
displays
interesting
borderline
case
between
ring
expansion
and
coordination,
while
stibenium
afford
addition
Tuning
steric
electronic
properties
ion
shows
a
drastic
influence
reaction
outcome.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(63)
Опубликована: Авг. 14, 2023
Abstract
The
carbide
ligand
in
the
iron–molybdenum
cofactor
(FeMoco)
nitrogenase
bridges
iron
atoms
different
oxidation
states,
yet
it
is
difficult
to
discern
its
ability
mediate
magnetic
exchange
interactions
due
structural
complexity
of
cofactor.
Here,
we
describe
two
mixed‐valent
diiron
complexes
with
C‐based
ketenylidene
bridging
ligands,
and
compare
carbon
more
familiar
sulfur
bridges.
ground
state
[Fe
2
(μ‐CCO)
]
+
complex
(
4
)
S
=
,
valence
delocalized
on
Mössbauer
timescale
a
small
thermal
barrier
for
electron
hopping
that
stems
from
low
Fe−C
force
constant.
In
contrast,
one‐electron
reduction
(μ‐CCO)]
one
bridge
affords
mixed‐valence
species
high‐spin
),
Fe−Fe
distance
contracts
by
1
Å.
Spectroscopic,
magnetic,
computational
studies
latter
reveal
an
bonding
interaction
leads
complete
delocalization.
Analysis
near‐IR
intervalence
charge
transfer
transitions
5
indicates
very
large
double
constant
B
range
780–965
cm
−1
.
These
results
show
are
extremely
effective
at
stabilizing
states
dimers.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(48)
Опубликована: Окт. 14, 2023
Due
to
their
limited
capacity
for
π-backdonation,
isolation
of
π-complexes
main-group
elements
remains
a
great
challenge.
We
report
herein
the
synthesis
homoleptic
diphosphene
lead
complex
(2)
from
degradation
P4
with
bis(germylene)-stabilized
Pb(0)
complex.
Structural
and
computational
studies
showed
that
2
possesses
significant
π
bonding
interactions
between
Pb
atom
ligands,
which
is
reminiscent
transition-metal
complexes.
Consistent
its
unique
electronic
structure,
can
deliver
atoms
perform
redox
reaction
an
iminoquinone
produce
cyclic
plumbylene
(4)
2,5-dimethyl-3,4-dimethylimidazol-1-ylidene
(IMe2
Me2
)
induced
phosphorus
cation
abstraction
give
anionic
PbP3
(6).
Chemical Communications,
Год журнала:
2023,
Номер
59(67), С. 10117 - 10120
Опубликована: Янв. 1, 2023
A
systematic
study
on
the
reactivity
of
cyclo-P4
complexes
[CpRTa(CO)2(η4-P4)]
towards
pnictogenium
cations
results
in
formation
functionalised
interpnictogen
cations.
Phosphenium
ions
insert
into
one
P-P
bonds
to
give
ring-expanded
cyclo-P5R2
products.
In
contrast,
an
arsenium-functionalised
P4AsCy2
ligand
displays
interesting
borderline
case
between
ring
expansion
and
coordination,
while
stibenium
afford
addition
Tuning
steric
electronic
properties
ion
shows
a
drastic
influence
reaction
outcome.
