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Functionalized nickel()-iron() dithiolates as biomimetic models of [NiFe]-Hases
To develop the structural and functional modeling chemistry of [NiFe]-H 2 ases, a series of new biomimetics for the active site of [NiFe]-H 2 ases have been prepared by various synthetic methods. Treatment of the mononuclear Ni complex (pnp)NiCl 2 (pnp = (Ph 2 PCH 2 ) 2 NPh) with (dppv)Fe(CO) 2 (pdt...
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| Published in: | Dalton transactions : an international journal of inorganic chemistry 2023-03, Vol.52 (12), p.3755-3768 |
|---|---|
| Main Authors: | , , , |
| Format: | Article |
| Language: | |
| Online Access: | Get full text |
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| Summary: | To develop the structural and functional modeling chemistry of [NiFe]-H
2
ases, a series of new biomimetics for the active site of [NiFe]-H
2
ases have been prepared by various synthetic methods. Treatment of the mononuclear Ni complex (pnp)NiCl
2
(pnp = (Ph
2
PCH
2
)
2
NPh) with (dppv)Fe(CO)
2
(pdt) (dppv = 1,2-(Ph
2
P)
2
C
2
H
2
, pdt = 1,3-propanedithiolate) and KPF
6
gave the dicarbonyl complex [(pnp)Ni(pdt)Fe(CO)
2
(dppv)](PF
6
)
2
([
1
](PF
6
)
2
). Further treatment of [
1
](PF
6
)
2
and [(dppe)Ni(pdt)Fe(CO)
2
(dppv)](BF
4
)
2
(dppe = 1,2-(Ph
2
P)
2
C
2
H
4
) with the decarbonylation agent Me
3
NO and pyridine afforded the novel sp
3
C-Fe bond-containing complexes [(pnp)Ni(SCH
2
CH
2
CHS)Fe(CO)(dppv)]PF
6
([
2
]PF
6
) and [(dppe)Ni(SCH
2
CH
2
CHS)Fe(CO)(dppv)]BF
4
([
3
]BF
4
). More interestingly, the first
t
-carboxylato complexes [(pnp)Ni(pdt)Fe(CO)(
t
-O
2
CR)(dppv)]PF
6
([
4
]PF
6
, R = H; [
5
]PF
6
, R = Me; [
6
]PF
6
, R = Ph) could be prepared by reactions of [
1
]PF
6
with the corresponding carboxylic acids RCO
2
H in the presence of Me
3
NO, whereas further reactions of [
4
]PF
6
-[
6
]PF
6
with aqueous HPF
6
and 1.5 MPa H
2
gave rise to the μ-hydride complex [(pnp)Ni(pdt)Fe(CO)(μ-H)(dppv)]PF
6
([
7
]PF
6
). Except for H
2
activation by
t
-carboxylato complexes [
4
]PF
6
-[
6
]PF
6
to give a μ-hydride complex ([
7
]PF
6
), the sp
3
C-Fe bond-containing complex [
2
]PF
6
was found to be a catalyst for proton reduction to H
2
under CV conditions. Furthermore, the chemical reactivity of the μ-hydride complex [
7
]PF
6
displayed in the e
−
transfer reaction with FcPF
6
in the presence of CO, the H
2
evolution reaction with the protonic acid HCl, and the H
−
transfer reaction with
N
-methylacridinium hexafluorophosphate ([NMA]PF
6
) was systematically studied. As a result, a series of the expected products such as H
2
, ferrocene, the dicarbonyl complex [
1
](PF
6
)
2
, the μ-chloro complex [(pnp)Ni(pdt)Fe(CO)(μ-Cl)(dppv)]PF
6
([
8
]PF
6
), the
t
-MeCN-coordinated complex [(pnp)Ni(pdt)Fe(CO)(
t
-MeCN)(dppv)](PF
6
)
2
([
9
](PF
6
)
2
) and the H
−
transfer product AcrH
2
were produced. While all the newly prepared model complexes were structurally characterized by spectroscopic methods, the molecular structures of some of their representatives were confirmed by X-ray crystallography.
The syntheses, structures and chemical reactivity of a series of new butterfly Ni
II
Fe
II
(μ-S)
2
core-containing [NiFe]-H
2
ase models have been investigated. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/d3dt00039g |