Within only five minutes at 20°C bimetallic fulvalene complexes 1 undergo intramolecular disproportionation in the presence of PMe3 or P(OMe)3 when electron‐reservoir complexes of the type [FeICp(arene)] serve as catalysts. MI = Mo, W, Fe, Ru; M2 = Mo, W; n = 2, 3; m = 3; arene = C6H6, C6Me6. The heterodinuclear complexes react with regioselectivity.
The C-0 bond of Fe(q5-C5H5)+ complexes of aryl ethers is cleaved smoothly by reaction of ButOK in THF or KOH in DME, yielding n-phenate complexes; transetherification can also be achieved in situ at room temperature.
The bi-sandwich complex
[Fe2Fv(C6H6)2]2+(PF6
-)2
(1
2+; Fv =
μ2-η5:η5-fulvalenyl, unless
noted
otherwise) synthesized from biferrocene, was photolyzed with visible
light in acetonitrile in
the presence of 1,2-bis(diphenylphosphino)ethane (dppe) or
bis(diphenylphosphino)methane
(dppm) at −15 °C to give
[Fe2Fv(dppe)2(NCMe)2]2+(PF6
-)2
(2a
2+) or
[Fe2Fv(dppm)2(NCMe)2]2+(PF6
-)2
(2b
2+). The complexes
2a
2+ and 2b
2+ reacted
in refluxing 1,2-dichloroethane with CO to give
[Fe2Fv(dppe)2(CO)2]2+(PF6
-)2
(3a
2+) and
[Fe2Fv(dppm)2(CO)2]2+(PF6
-)2
(3b
2+), and 2a
2+
reacted similarly with PMe3 to give
[Fe2Fv(dppe)2(PMe3)]2+(PF6
-)2
(4
2+).
The direduced 38-electron (38e) complex 1 reacted at
−15 °C with 1 atm of CO to give [Fe2(μ2-η4:η4-Fv)(CO)6]
(7) and with PMe3 to give
[Fe2Fv(PMe3)4]
(9). When
Na+PF6
- was
present
in stoichiometric amounts in THF, these reactions followed a different
course and
Na+PF6
-
induced electron transfer (disproportionation) by irreversibly
dislocating ion pairs: the
reaction of 1 with 1 atm of CO gave
[Fe(η5-Fv)(η6-C6H6),
Na+PF6
-] (5),
and that with PMe3
gave
[Fe2Fv(PMe3)6]2+(PF6
-)2
(8
2+) and the known complex
[Fe(PMe3)4] (10). The
cyclic
voltammograms (CV) of 2a
2+ and
2b
2+ contain irreversible oxidation and
reduction waves,
but the CVs of 3a
2+ and
3b
2+ showed two close reversible
monoelectronic reduction waves
(no oxidation wave). The CVs of the hexaphosphine complexes
indicated partially or fully
irreversible reduction waves, respectively, but two reversible waves at
+0.71 and +0.95 V
for 4
2+ and +0.70 and +1.08 V for
8
2+ (vs SCE, Pt, DMF, 0.1 M
n-Bu4NBF4 −30 °C).
The
bielectronic reduction of 2a
2+ and the
bielectronic oxidation of 4
2+ and
8
2+ using redox
reagents led to decomposition, but the monoelectronic oxidation of
4
2+ and 8
2+ using
(p-Br-C6H4)3N+SbCl6
-
in CH2Cl2 gave the stable mixed-valence
trications 4
3+
and
8
3+
, for which
the Mössbauer spectra showed delocalized average valency on the
Mössbauer time scale.
These studies have opened the route to a variety of mono- and
diiron fulvalenyl organometallic compounds, confirming the great importance of the presence of
Na+PF6
-. This
salt
can change reaction pathways and, in particular, induce
electron-transfer reactions,
underlining the extraordinary electronic flexibility of the fulvalenyl
ligand and its ability to
transfer the electron flow between two metal centers.
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