Successive insertion of tetrafluoroethylene and CO and of
tetrafluoroethylene and acetylenes into aryne–nickel(0)
bonds
Abstract
Aryne–nickel complexes
[Ni(η
2
-C
6
H
4
)L
2
]
[L
2
= 2PEt
3
or dcpe;
dcpe = (C
6
H
11
)
2
PCH
2
CH
2
P(C
6
H
11
)
2
] and
[Ni(η
2
-C
10
H
6
)(PEt
3
)
2
] reacted readily with C
2
F
4
to form
the corresponding five-membered tetrafluoro-substituted nickelacycles
[![[upper bond 1 start]](https://www.rsc.org/images/entities/char_e010.gif)
Ni(C
6
H
4
CF
2
C![[upper bond 1 end]](https://www.rsc.org/images/entities/char_e011.gif)
F
2
-2)L
2
] (L
2
= dcpe or
2PEt
3
) and
[Ni(2-C
10
H
6
CF
2
CF
2
-3)(PEt
3
)
2
], respectively. The complex
[Ni(C
6
H
4
CF
2
CF
2
-2)(dcpe)] is very stable towards air, whereas the PEt
3
analogues react readily to give µ-aryloxo dimers. The
naphthalene-based dimer
[{Ni(µ-2-OC
10
H
6
CF
2
CF
2
-3)(PEt
3
)}
2
] has
been structurally characterized. The complexes
[Ni(C
6
H
4
CF
2
CF
2
-2)L
2
] insert CO into their aryl–nickel bonds to
form six-membered acyl complexes
[Ni{C(O)C
6
H
4
CF
2
C
F
2
-2}L
2
] (L
2
= dcpe
or 2PEt
3
) and, after CO-induced reductive elimination,
2,2,3,3-tetrafluoroindanone. The dcpe acyl complex has also been shown
to undergo reaction with air to form the carboxylato complex
[Ni{OC(O)C
6
H
4
CF
2
C
F
2
-2}(dcpe)], whose structure has been confirmed by
X-ray crystallography. Some insertions of acetylenes into the
aryl–nickel bonds of
[Ni(C
6
H
4
CF
2
CF
2
-2)L
2
] are also reported.
Ni(C
6
H
4
CF
2
CF
2
-2)L
2
] (L
2
= dcpe or
2PEt
3
) and
[Ni(2-C
10
H
6
CF
2
CF
2
-3)(PEt
3
)
2
], respectively. The complex
[Ni(C
6
H
4
CF
2
CF
2
-2)(dcpe)] is very stable towards air, whereas the PEt
3
analogues react readily to give µ-aryloxo dimers. The
naphthalene-based dimer
[{Ni(µ-2-OC
10
H
6
CF
2
CF
2
-3)(PEt
3
)}
2
] has
been structurally characterized. The complexes
[Ni(C
6
H
4
CF
2
CF
2
-2)L
2
] insert CO into their aryl–nickel bonds to
form six-membered acyl complexes
[Ni{C(O)C
6
H
4
CF
2
C
F
2
-2}L
2
] (L
2
= dcpe
or 2PEt
3
) and, after CO-induced reductive elimination,
2,2,3,3-tetrafluoroindanone. The dcpe acyl complex has also been shown
to undergo reaction with air to form the carboxylato complex
[Ni{OC(O)C
6
H
4
CF
2
C
F
2
-2}(dcpe)], whose structure has been confirmed by
X-ray crystallography. Some insertions of acetylenes into the
aryl–nickel bonds of
[Ni(C
6
H
4
CF
2
CF
2
-2)L
2
] are also reported.
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