Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 4, 2025
The
design
of
cobalt
complexes
for
the
hydrogen
evolution
reaction
(HER)
has
garnered
significant
attention
over
past
few
decades.
To
address
limitations
traditional
trial-and-error
method,
we
introduced
strategy
a
simplified
mechanism-based
approach
with
data-driven
practice
(SMADP)
in
this
study.
Our
results
indicate
that
polypyridyl
DPA-Bpy
family
(DPA-Bpy
=
N,N-bis(2-pyridinylmethyl)-2,2′-bipyridine-6-methanamine)
generally
follow
electron
transfer
(E)–chemical
proton
(C)–electron
(C)
pathway
HER.
However,
involvement
proton-coupled
(PCET)
formation
[CoII(L)–H]+
intermediate
been
observed
PY5Me2
(PY5Me2
2,6-bis(1,1-di(pyridin-2-yl)ethyl)pyridine).
Furthermore,
hydricity
(ΔGH–)
and
CoIII–H/CoII–H
reduction
potential
(ERed°)
are
found
to
be
active
descriptors
cobalt-catalyzed
Excellent
two-parameter
regression
models
(ΔGH–
ERed°)
H2
molecule
have
obtained
(R2
0.9429
R2
0.9854
family).
demonstrate
SMADP
is
groundbreaking
method
delineating
This
could
also
accelerate
novel
enhanced
Dalton Transactions,
Journal Year:
2024,
Volume and Issue:
53(37), P. 15421 - 15426
Published: Jan. 1, 2024
Mononuclear
Fe(III)
complexes
containing
an
antipyrine
Schiff
base
ligand
were
prepared
and
fully
characterized,
demonstrating
a
planar
tetradentate
coordination
geometry.
These
found
to
be
active
for
the
hydrogen
evolution
reaction.
Catalysis
occurs
at
-1.4
V
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(52)
Published: Nov. 18, 2024
Abstract
The
active
sites
of
metalloenzymes
involved
in
small
molecules
activation
often
contain
pendant
bases
that
act
as
proton
relay
promoting
proton‐coupled
electron‐transfer
processes.
Here
we
focus
on
hydrogenases
and
the
reactions
they
catalyze,
i.
e.
hydrogen
evolution
oxidation
reactions.
After
a
short
description
these
enzymes,
review
some
various
biomimetic
bioinspired
molecular
systems
relays.
We
then
provide
formal
electrochemical
framework
required
to
decipher
key
role
such
enhance
catalysis
single
direction
discuss
few
for
H
2
which
quantitative
kinetic
data
are
available.
finally
highlight
parameters
reach
bidirectional
(both
catalyzed)
transition
reversible
catalyzed
narrow
potential
range)
well
illustrate
features
from
literature.
The Journal of Physical Chemistry C,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 25, 2024
Ligand
type
and
ligand
coordination
around
cobalt
photocatalysts
influence
the
reaction
mechanism
of
H2
production
via
water
splitting.
We
investigated
mechanisms
a
bis-bipyridyl
planar
reduction
catalyst
in
an
aqueous
solution
using
ab
initio
molecular
dynamics,
metadynamics,
density
functional
theory,
free
energy
perturbation
theory.
Modeling
each
intermediate
step
reveals
that
cobalt-based
exhibits
preference
for
pathway
involving
two
successive
reductions,
followed
by
protonation
steps.
The
reason
this
is
presence
barrier
conformational
change
molecules
first
solvation
shell
following
reduction.
This
prevents
direct
with
protons,
which
necessary
initial
sequential
electron-
proton-transfer
mechanisms.
In
reductions
protonations,
however,
second
facilitates
interaction
between
enabling
protonation.
Following
mechanism,
produced
released
into
solvent.
Reduction
calculations
reveal
that,
reduction,
singlet
spin
state
system
more
favorable
than
triplet
state.
electron
transfer
0.19
eV
less
energetic
reaction.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(52)
Published: Nov. 18, 2024
Abstract
The
active
sites
of
metalloenzymes
involved
in
small
molecules
activation
often
contain
pendant
bases
that
act
as
proton
relay
promoting
proton‐coupled
electron‐transfer
processes.
Here
we
focus
on
hydrogenases
and
the
reactions
they
catalyze,
i.
e.
hydrogen
evolution
oxidation
reactions.
After
a
short
description
these
enzymes,
review
some
various
biomimetic
bioinspired
molecular
systems
relays.
We
then
provide
formal
electrochemical
framework
required
to
decipher
key
role
such
enhance
catalysis
single
direction
discuss
few
for
H
2
which
quantitative
kinetic
data
are
available.
finally
highlight
parameters
reach
bidirectional
(both
catalyzed)
transition
reversible
catalyzed
narrow
potential
range)
well
illustrate
features
from
literature.
