Alkynyl-Phosphine Substituted Fe2S2 Clusters: Synthesis, Structure and Spectroelectrochemical Characterization of a Cluster with a Class III Mixed-Valence [FeFe]3+ Core
Phosphinoalkynes P(C≡CC 6 H 4 Me-4)Ph 2 ( 1 ) and P(C≡CC 6 H 4 C≡CC 6 H 4 Me-4)Ph 2 ( 2 ) have been prepared from CuI catalysed reactions of the corresponding 1-alkyne and PClPh 2 . The trimethylamine- N -oxide promoted reaction of PPh 3 , 1 or 2 with [Fe 2 (μ-pdt)(CO) 6 ] (pdt = propanedithiolate)...
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| Published in: | Journal of cluster science Vol. 26; no. 1; pp. 233 - 246 |
|---|---|
| Main Authors: | , , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
Boston
Springer US
2015
Springer Nature B.V |
| Subjects: | |
| Online Access: | Get full text |
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| Summary: | Phosphinoalkynes P(C≡CC
6
H
4
Me-4)Ph
2
(
1
) and P(C≡CC
6
H
4
C≡CC
6
H
4
Me-4)Ph
2
(
2
) have been prepared from CuI catalysed reactions of the corresponding 1-alkyne and PClPh
2
. The trimethylamine-
N
-oxide promoted reaction of PPh
3
,
1
or
2
with [Fe
2
(μ-pdt)(CO)
6
] (pdt = propanedithiolate) affords derivatives [Fe
2
(μ-pdt)(CO)
5
{PRPh
2
}] [R=Ph (
3
), C≡CC
6
H
4
Me (
5
), C≡CC
6
H
4
C≡CC
6
H
4
Me (
6
)] or, at elevated temperatures, [Fe
2
(μ-pdt)(CO)
4
(PPh
3
)
2
] (
4
). The cyclic voltammograms of compounds
3
and
4
feature almost fully reversible one-electron oxidation processes and an irreversible reduction, whilst the electrochemical response of the alkynyl phosphine substituted complexes
5
and
6
is irreversible for both oxidation and reduction. IR spectroelectrochemical studies of
4
are consistent with an oxidation processes leading to a delocalized or (Class III) mixed valence [FeFe]
3+
core in which the iron centers have an average oxidation state of 1.5. The molecular structures of the alkynyl phosphine substituted clusters
5
and
6
are also reported. |
|---|---|
| ISSN: | 1040-7278 1572-8862 |
| DOI: | 10.1007/s10876-014-0790-5 |