Inorganic Chemistry,
Год журнала:
2023,
Номер
62(51), С. 21083 - 21090
Опубликована: Дек. 5, 2023
10-VE
A≡A'
Diatomics,
such
as
N≡N,
C≡O,
etc.,
have
a
strong
σ2π4
triple
bond
plus
lone
pair
at
each
end.
In
our
studies
on
14-VE
A≡B
systems,
C≡Pt,
we
find
similar
bonding
system
(5dδ)4
ring.
Here,
the
A
atom
belongs
to
groups
13-17
and
B
7-11.
Also
BB'
combinations,
triatomics,
PtCO
or
DsCO
uranyl,
longer
chains,
AuCN
[NC-Au-CN]-,
are
discussed.
The
δ
ring
directly
contributes
nuclear
quadrupole
coupling
constants,
DFT
calculations
using
BH
H
mPW1K
functionals
reproduce
experimental
trends
of
NQCC.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(18), С. 12790 - 12798
Опубликована: Апрель 29, 2024
Research
on
metal–metal
bonds
involving
f-block
actinides,
such
as
thorium,
lags
far
behind
the
well-studied
of
d-block
transition
metals.
The
complexes
with
Th–TM
are
extremely
rare;
all
previously
identified
examples
have
only
a
single
bond
Th
center
at
an
invariably
+IV
oxidation
state.
Herein,
we
report
series
Th2Pdn
(n
=
2,
3,
and
6)
clusters
(complexes
4,
7)
multiple
Th(III)–Pd
bonds.
Theoretical
studies
reveal
that
unit
allows
electronic
delocalization
σ
aromaticity,
leading
to
unexpected
closed-shell
singlet
structures
for
these
Th(III)
species.
This
is
evident
in
highest
occupied
molecular
orbital
facilitates
2e
reduction
alkyne
by
complex
7,
resulting
formation
8.
Complexes
7
8
distinctive
featuring
Th2Pd6
core
six
eight
Th–Pd
bonds,
respectively,
making
them
largest
known
d–f
heterometallic
exhibiting
bonding.
Organometallics,
Год журнала:
2025,
Номер
44(1), С. 354 - 362
Опубликована: Янв. 1, 2025
The
investigation
of
metal–metal
bonds
involving
f-block
actinides
has
significantly
lagged
behind
extensive
research
on
d-block
transition
metal
bonds.
Species
featuring
thorium-transition
are
exceptionally
rare.
In
this
study,
we
report
the
synthesis
first
species
containing
Th–Rh
Using
two
nitrogen–phosphorus
ligands,
[CH3N(CH2CH2NHPiPr2)2]
and
{[CH2O(CH2)2NHPiPr2]2},
synthesized
Th(IV)
chloride
precursors
1
5.
Reactions
precursor
with
[RhCl(COD)]2
or
[IrCl(COD)]2
at
room
temperature
produced
heterometallic
clusters
2
3,
respectively.
Similarly,
5
reacted
under
same
conditions
to
yield
analogues
6
7.
Notably,
heating
complexes
90
°C
led
formation
4
8,
each
bonding
interactions.
interaction
in
complex
8
is
stronger
than
that
7,
as
confirmed
by
both
experimental
observations
theoretical
analysis.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 16, 2025
Abstract
Although
complexes
with
monatomic
zero-valent
main
group
centers
have
been
reported,
diatomic
are
extremely
rare
and
all
previously
reported
examples
were
stabilized
by
either
carbene
or
silylene
ligands.
Here,
we
present
the
isolation
of
E(0)-E(0)
(E
=
Sn,
Pb)
species
supported
two
[N{CH₂CH₂NP
i
Pr₂}₃Sn]
fragments.
The
reaction
trilithium
salt
N{CH
2
CH
NLiP
Pr
}
3
SnCl
yields
complex
[N{CH
NP
]
Sn
(
1
)
a
chain.
reduction
mixture
KC
8
produces
catenated
4
chain
),
featuring
Sn(0)-Sn(0)
unit.
Further
alkali
metal
ion-bridged
SnK]
).
Moreover,
PbI
affords
SnPb]
which
can
also
be
generated
SnLi]
5
Complex
features
Pb(0)-Pb(0)
unit,
representing
heavy
complex.
presence
units
in
,
respectively,
is
further
confirmed
computational
studies.
Inorganic Chemistry,
Год журнала:
2023,
Номер
62(39), С. 16077 - 16083
Опубликована: Сен. 21, 2023
Ligands
are
known
to
play
a
crucial
role
in
the
construction
of
complexes
with
metal–metal
bonds.
Compared
bonds
involving
d-block
transition
metals,
knowledge
f-block
rare-earth
metals
still
lags
far
behind.
Herein,
we
report
series
cerium–transition-metal
bonds,
which
supported
by
two
kinds
nitrogen–phosphorus
ligands
N[CH2CH2NHPiPr2]3
(VI)
and
PyNHCH2PPh2
(VII).
The
reactions
zerovalent
group
10
metal
precursors,
Pd(PPh3)4
Pt(PPh3)4,
cerium
complex
VI
generate
heterometallic
clusters
[N{CH2CH2NPiPr2}3Ce(μ-M)]2
(M
=
Pd,
2
M
Pt,
3)
featuring
four
Ce–M
bonds;
meanwhile,
bimetallic
species
[(PyNCH2PPh2)3Ce-M]
Ni,
5;
6;
7)
single
bond
were
isolated
from
precursor
4
VII
Ni(COD)2,
Pd(PPh3)4,
or
respectively.
These
represent
first
example
an
RE–M
between
Ce
3
contain
largest
number
donor/acceptor
interactions
ever
have
been
observed
molecule.
Inorganic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(19), С. 5622 - 5633
Опубликована: Янв. 1, 2023
A
monoanionic
N–P
ligand
L3
with
a
pendant
dimethylamino
group
was
designed.
Species
multiple
U–C
bonds—a
rare
example
of
metallafluorene
containing
an
actinide
element—and
clusters
U–M
bonds
were
isolated.
