Synthesis of fluorophenyl derivatives of iron, molybdenum and tungsten via B(C6F5)3 and unusual carbon–fluorine bond reactions
Abstract
The reaction between B(C
6
F
5
)
3
and
[Fe(η-C
5
H
5
)(CO)
2
Me] gave the
unexpected product
[Fe{C
6
F
4
C(O)Me-2}(η-C
5
H
5
)(CO)] 1 which reacts with the donor molecules
L = PMe
3
, PPh
3
or Bu
t
NC
giving
[Fe{C
6
F
4
C(O)Me-2}(η-C
5
H
5
)L].* Likewise
[{Fe[C
6
F
4
C(O)Me-2](η-C
5
H
5
)}
2
(µ-dppe)]* was formed from 1 and
Ph
2
P(CH
2
)
2
PPh
2
(dppe). The
formation of the compound where L = PMe
3
is
shown to proceed via initial formation of
[Fe{C
6
F
4
C(O)Me-2}(η-C
5
H
5
)(CO)(PMe
3
)]*. The reaction between
B(C
6
F
5
)
3
and
[M(η-C
5
H
5
)(CO)
3
Me]
(M = Mo or W) gave the compounds
[M{C
6
F
4
C(O)Me-2}(η-C
5
H
5
)(CO)
2
]. The compounds
[M{C
6
F
3
X-5-C(O)Me-2}(η-C
5
H
5
)(CO)
2
]* (M = Mo or W) where
X = H were prepared from the compounds where
X = F via unusual C–F bond-activation
reactions. The compound
[Fe{C
6
F
3
H-5-C(O)Me-2}(η-C
5
H
5
)(PMe
3
)] was prepared by photolysis of a
mixture of
[Fe{C
6
F
3
H-5-C(O)Me-2}(η-C
5
H
5
)(CO)] and PMe
3
. The asterisk indicates
the crystal structure has been determined.
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