Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(36)
Published: July 6, 2023
Abstract
Der
bimetallische,
dekanukleare
Ni
3
Ga
7
‐Cluster
[Ni
(GaTMP)
(
μ
2
‐GaTMP)
‐GaTMP)]
1
,
TMP=2,2,6,6‐
Tetramethylpiperidinyl)
reagiert
reversibel
mit
Wasserstoff
unter
Bildung
einer
Reihe
von
(Poly‐)Hydridclustern
.
Tieftemperatur‐2D
NMR‐Experimente
bei
−80
°C
zeigen,
dass
aus
einem
Gemisch
Di‐
Di
),
Tetra‐
Tetra
)
und
Hexahydrid‐Spezies
Hexa
besteht.
Die
Strukturen
werden
durch
eine
Kombination
2D
NMR‐Spektroskopie
DFT‐Berechnungen
untersucht.
Das
Zusammenspiel
beider
Metalle
ist
für
die
hohe
Wasserstoffinkorperierung
des
Clusters
entscheidend.
Polyhydride
sind
der
Semihydrierung
4‐Octin
zu
4‐Octen
guter
Selektivität
katalytisch
aktiv.
Bei
handelt
es
sich
um
erste
Spezies
ihrer
Art,
Eigenschaften
molekularen,
atomgenauen
Übergangsmetall‐/Hauptgruppenmetallclustern
konzeptionell
entsprechenden
Festkörperphase
in
Katalyse
verbindet.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
16(2)
Published: Nov. 6, 2023
Abstract
Single‐site
catalysis
is
an
increasingly
vital
strategy
to
optimise
heterogeneous
catalytic
reactions.
In
ideal
case,
the
nature
and
population
of
catalytically
active
sites
are
all
identical,
which
impossible
realise
on
a
solid
support.
The
idea
single
site
catalysts
transferred
from
homogeneous
by
incorporation
transition
metal
with
oxidation
state
0
in
surface
small,
soluble,
molecular,
homoatomic
germanium
atom
cluster
that
also
comprises
main
group
atoms
close
zero.
An
optimised
synthetic
protocol
for
four
compounds
Hyp
3
Et[Ge
9
Ni]PR
(R=Ph,
p
tolyl,
i
Pr,
Me)
presented,
embedded
Ge
polyhedral
cluster.
products
were
characterised
NMR
spectroscopy,
LIFDI/MS
elemental
analysis
structurally
R=
Pr
Me
crystal
X‐ray
structure
determination
comprising
closo
‐[Ge
Ni]
core.
potential
investigated
various
olefin
isomerisation
formation
realized
ligand
dissociation,
observed
PPh
.
DFT
calculations
Me),
Ni](tolyl)
Ni](C
6
H
12
)
show
exchange
substrate
molecules
occurs
during
reaction.
Since
same
principle,
namely
bare
at
surface,
applies
as
single‐site
since
contrast
classical
abbreviation
SSHoC
S
ingle
ite
Ho
mogeneous
C
atalyst
proposed
this
catalyst
type.
each
active,
enable
considerable
increase
efficiency
thus
allow
sustainable
use
expensive
less
abundant
metals.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(6), P. 1247 - 1247
Published: March 11, 2025
The
incorporation
of
transition
metal
atoms
into
[Ge9]
clusters
is
a
widely
studied
area
Zintl-cluster
chemistry.
Recently,
it
was
shown
that
comprising
single
in
the
cluster
surface
show
catalytic
properties.
Here,
we
present
synthetic
approach
to
four
new
compounds
silylated
Ge9
with
organometallic
ruthenium
complexes.
[η5-Ge9Hyp3]RuCp*
(1),
[η1-Ge9(SitBu2H)3]RuCp(PPh3)2
(2),
and
[Hyp3Ge9][RuCp(PPh3)2(MeCN)]
(3b)
(Cp
=
cyclopentadienyl,
Cp*
pentamethylcyclopentadienyl,
Hyp
Si(SiMe3)3,
Ph
C6H5,
tBu
tert-butyl)
were
characterized
by
means
NMR
spectroscopy
single-crystal
structure
determination.
In
case
2,
isomer
an
approximated
C4v
symmetric
monocapped
square
antiprism
nine
Ge
unexpected
ligand
arrangement
three
ditertbutylsilane
ligands
attached
open
obtained.
[Hyp3Ge9][RuCp(PPh3)2]
(3a)
via
LIFDI
mass
spectrometry.
Overall,
able
steric
demand
Cp
vs.
hypersilylchloride
strongly
influence
on
cluster.
addition,
solvent
also
affects
cluster,
as
appears
atom
3a
dissociates
from
upon
acetonitrile
coordination
form
3b.
These
results
choosing
right
tools
makes
big
difference
outcome
metalation
reaction.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 6386 - 6409
Published: April 4, 2025
Nuclear
spin
hyperpolarization
utilizing
parahydrogen
has
the
potential
for
broad
applications
in
chemistry,
catalysis,
biochemistry,
and
medicine.
This
review
examines
recent
chemical
biochemical
insights
gained
using
parahydrogen-induced
polarization
(PHIP).
We
begin
with
photoinduced
PHIP,
which
allows
investigation
of
short-lived
photoactivated
catalysis.
Next,
we
partially
negative
line
effect,
distinctive
shape
helps
to
reveal
information
about
rapid
exchange
role
catalytic
species.
The
NMR
signal
enhancement
a
single
proton
oneH-PHIP
is
discussed,
challenging
underpinning
concept
necessity
pairwise
hydrogenation.
Furthermore,
examine
metal-free
PHIP
facilitated
by
frustrated
Lewis
pair
molecular
tweezers
radicaloids,
demonstrating
alternative
routes
Although
symmetric
molecules
incorporating
are
silent,
showcase
methods
that
hyperpolarized
states
through
post-hydrogenation
reactions.
discuss
processes
mediate
transfer
between
target,
expanding
reach
without
synthesizing
specialized
precursors.
conclude
this
highlighting
uncovering
H2
activation
mechanisms
hydrogenases.
By
providing
detailed
these
diverse
phenomena,
aim
familiarize
reader
versatility
its
mechanistic
studies
analysis.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(46), P. 21213 - 21223
Published: Nov. 9, 2022
The
first
fully
characterized
boron-functionalized
heptaphosphide
Zintl
cluster,
[(BBN)P7]2-
([1]2-),
is
synthesized
by
dehydrocoupling
[HP7]2-.
Dehydrocoupling
a
previously
unprecedented
reaction
pathway
to
functionalize
clusters.
[Na(18-c-6)]2[1]
was
employed
as
transition
metal-free
catalyst
for
the
hydroboration
of
aldehydes
and
ketones.
Moreover,
greenhouse
gas
carbon
dioxide
(CO2)
efficiently
selectively
reduced
methoxyborane.
This
work
represents
examples
catalysis
where
transformation
cluster
noninnocent.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(36)
Published: July 6, 2023
The
bimetallic,
decanuclear
Ni3
Ga7
-cluster
of
the
formula
[Ni3
(GaTMP)3
(μ2
-GaTMP)3
(μ3
-GaTMP)]
(1,
TMP=2,2,6,6-tetramethylpiperidinyl)
reacts
reversibly
with
dihydrogen
under
formation
a
series
(poly-)hydride
clusters
2.
Low-temperature
2D
NMR
experiments
at
-80
°C
show
that
2
consist
mixture
di-
(2Di
),
tetra-
(2Tetra
)
and
hexahydride
species
(2Hexa
).
structures
2Di
2Tetra
are
assessed
by
combination
spectroscopy
DFT
calculations.
cooperation
both
metals
is
essential
for
high
hydrogen
uptake
cluster.
Polyhydrides
catalytically
active
in
semihydrogenation
4-octyne
to
4-octene
good
selectivity.
example
first
its
kind
conceptually
relates
properties
molecular,
atom-precise
transition
metal/main
group
metal
respective
solid-state
phase
catalysis.
Dalton Transactions,
Journal Year:
2023,
Volume and Issue:
52(38), P. 13787 - 13796
Published: Jan. 1, 2023
Despite
p-block
clusters
being
known
for
over
a
century,
their
application
as
catalysts
to
mediate
organic
transformations
is
underexplored.
Here,
the
boron
functionalized
[P7]
cluster
[(BBN)P7]2-
([1]2-;
BBN
=
9-borabicyclo[3.3.1]nonane)
applied
in
dearomatized
reduction
of
pyridines,
well
hydroboration
imines
and
nitriles.
These
afford
amine
products,
which
are
important
precursors
pharmaceuticals,
agrochemicals,
polymers.
Catalyst
[1]2-
has
high
stability
these
reductions:
recycling
nine
times
quinoline
led
virtually
no
loss
catalyst
performance.
The
can
also
be
recycled
between
two
different
transformations,
again
with
competency.
mechanism
pyridine
was
probed
experimentally
using
variable
time
normalization
analysis,
computationally
density
functional
theory.
This
work
demonstrates
that
Zintl
nitrogen
containing
substrates
transition
metal-free
manner.
Communications Chemistry,
Journal Year:
2023,
Volume and Issue:
6(1)
Published: June 5, 2023
Multimetallic
clusters
play
a
key
role
as
models
to
doped
metals,
candidates
new
types
of
superatomic
catalysts
and
precursors
multimetallic
solids.
Understanding
formation
pathways
is
an
essential
necessary
step
forward
in
the
development
cluster
synthesis
research,
yet
remains
considerably
lacking
owing
difficulty
identification
intermediates
ill-defined
nature
common
starting
materials.
Here
we
show
progress
this
regard
by
investigating
reactivity
intermetallic
solid
nominal
composition
'K5Ga2Bi4'
with
[W(cod)(CO)4]
upon
extraction
ethane-1,2-diamine
(en)
4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane
(crypt-222).
Several
polybismuthide
by-products
were
identified
along
reaction
pathway,
ultimately
forming
salt
[K(crypt-222)]3[µ:η3-Bi3{W(CO)3}2]∙en∙tol.
DFT
calculations
revealed
plausible
schemes
for
transformations
taking
place
mixture
providing
insight
into
complex
on
basis
situ
generation
Bi22-.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(23)
Published: Feb. 13, 2024
Abstract
Tetranuclear
cores
(M−E)
2
of
transition
metals
(M)
and
tetrylenes
(E
II
=Si,
Ge,
Sn)
are
key
motifs
in
homogeneous
heterogeneous
catalysis.
They
exhibit
a
continuum
M−M
E−E
bonding
within
the
inorganic
core
that
leads
to
variety
structures
for
which
there
no
specific
synthetic
methods.
Herein,
we
report
series
highly
reduced
[Ni
0
Ge
]
squares
solely
stabilized
by
bulky
terphenyl
(C
6
H
3
−2,6‐Ar
)
ligands,
provide
complementary
high‐yielding
syntheses.
Reactivity
studies
with
common
Lewis
bases
(carbene
CO)
evince
structure
can
be
transformed.
We
have
investigated
this
modification
computational
means,
offering
rationale
better
understand
across
these
clusters.
Trends in Chemistry,
Journal Year:
2024,
Volume and Issue:
6(7), P. 349 - 351
Published: April 29, 2024
Although
known
for
over
a
century,
only
now
are
Zintl
clusters
being
investigated
as
catalysts.
These
can
serve
intermediaries
between
discrete
molecules
and
bulk
solids,
allowing
them
to
act
atom-precise
models
whose
reactivity
may
map
onto
their
heterogeneous
counterparts.
Key
contributions
in
homogeneous
catalysis
discussed.
Dalton Transactions,
Journal Year:
2022,
Volume and Issue:
51(47), P. 18329 - 18336
Published: Jan. 1, 2022
Clusters
of
main
group
elements,
such
as
phosphorus,
arsenic,
germanium,
and
tin
-
called
Zintl
clusters
have
been
known
for
more
than
a
century.
However,
their
application
in
catalysis
is
largely
unknown.
Here,
we
tether
boranes
to
seven-atom
phosphorus
cluster
({C8H14}BCH2CH2SiMe2)3P7
(2)
demonstrate
Lewis
acid
proof-of-principle
that
boron
chemistry
can
be
mapped
onto
using
this
method.
Catalyst
2
was
employed
mediate
key
organic
transformations,
including
the
hydroboration
carbodiimides,
isocyanates,
ketones,
alkenes,
alkynes,
nitriles.
To
best
our
knowledge,
first
Zintl-based
an
innocent
platform
metal-free
catalysis.
By
chaining
boron,
its
treasure
chest
unlocked
at
these
clusters.
Hence,
beyond
method
could
find
applications
neutron
capture
therapy,
stimuli
responsive
materials,
cross-coupling,
frustrated
pair
functional
polymer
chemistries.