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Facile Access to Redox‐Active C 2 ‐Bridged Complexes with Half‐Sandwich Manganese End Groups
Abstract The dinuclear mixed‐valent complex [(MeC 5 H 4 )(dmpe)MnC 2 Mn(dmpe)(C 5 H 4 Me)] + [(η 2 ‐MeC 5 H 4 ) 3 Mn] − [ 1 ] + [ 2 ] − (dmpe=1,2‐bis(dimethylphosphanyl)ethane) was prepared by the reaction of [Mn(MeC 5 H 4 ) 2 ] with dmpe and Me 3 SnCCSnMe 3 . The reactions of [ 1 ] + [ 2 ] − with...
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| Published in: | Chemistry : a European journal 2004-10, Vol.10 (19), p.4872-4885 |
|---|---|
| Main Authors: | , , , , |
| Format: | Article |
| Language: | English |
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| Online Access: | Get full text |
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| Summary: | Abstract
The dinuclear mixed‐valent complex [(MeC
5
H
4
)(dmpe)MnC
2
Mn(dmpe)(C
5
H
4
Me)]
+
[(η
2
‐MeC
5
H
4
)
3
Mn]
−
[
1
]
+
[
2
]
−
(dmpe=1,2‐bis(dimethylphosphanyl)ethane) was prepared by the reaction of [Mn(MeC
5
H
4
)
2
] with dmpe and Me
3
SnCCSnMe
3
. The reactions of [
1
]
+
[
2
]
−
with K[PF
6
] and Na[BPh
4
] yielded the corresponding anion metathesis products [(MeC
5
H
4
)(dmpe)MnC
2
Mn(dmpe)(C
5
H
4
Me)][PF
6
] ([
1
][PF
6
]) and [(MeC
5
H
4
)(dmpe)MnC
2
Mn(dmpe)(C
5
H
4
Me)][BPh
4
] ([
1
][BPh
4
]). These mixed‐valent species can be reduced to the neutral form by reaction with Na/Hg. The obtained complex [(MeC
5
H
4
)(dmpe)MnC
2
Mn(dmpe)(C
5
H
4
Me)] (
1
) displays a triplet/singlet spin equilibrium in solution and in the solid state, which was additionally studied by DFT calculations. The diamagnetic dicationic species [(MeC
5
H
4
)(dmpe)MnC
2
Mn(dmpe)(C
5
H
4
Me)][PF
6
]
2
([
1
][PF
6
]
2
) was obtained by oxidizing the mixed‐valent complex [
1
][PF
6
] with one equivalent of [Fe(C
5
H
5
)
2
][PF
6
]. Both redox processes are fully reversible. The dinuclear compounds were characterized by NMR, IR, UV‐visible, and Raman spectroscopy, cyclic voltammetry, and magnetic susceptibility measurements. X‐ray diffraction studies were performed on [
1
][
2
], [
1
][PF
6
], [
1
][BPh
4
], and [
1
][PF
6
]
2
. |
|---|---|
| ISSN: | 0947-6539 1521-3765 |
| DOI: | 10.1002/chem.200400143 |