SCHEDULED MAINTENANCE
Polyhetero-ferrocenes and -ruthenocenes derived from the
1,4,2-diphosphastibolyl ring anion
[P2SbC2But2]-
Abstract
The complex [RuCl
2
(PPh
3
)
3
] reacted
with the 1,4,2-diphosphastibolyl ring anion
[P
2
SbC
2
Bu
t
2
]
-
(containing ca. 25% of the 1,2,4-triphospholyl anion
[P
3
C
2
Bu
t
2
]
-
) to produce a cocrystallised mixture (crystal structure) of two
isomers of
[Ru(η
5
-P
2
SbC
2
Bu
t
2
)
2
] with
[Ru(η
5
-P
2
SbC
2
Bu
t
2
)(η
5
-P
3
C
2
Bu
t
2
)]. Variable-temperature
31
P-{
1
H}
NMR studies on the mixture show one of the isomers and the last complex
to be fluxional at room temperature. It is believed that an interring
Sb · · ·
Sb interaction in the other isomer restricts its fluxionality in
solution. The reaction of
[P
2
SbC
2
Bu
t
2
]
-
with FeCl
2
yielded only one isomer of the
heteroferrocene complex
[Fe(η
5
-P
2
SbC
2
Bu
t
2
)
2
] which is also non-fluxional in solution and has a
similar oxidation potential to that of ferrocene itself. The
heteroruthenocene complexes
[Ru(η
5
-P
2
SbC
2
Bu
t
2
)(η
5
-C
5
R
5
)]
(R = H or Me) were prepared by treating
[Ru(η
5
-C
5
R
5
)(MeCN)
3
]
[PF
6
] (R = H or Me) with
[P
2
SbC
2
Bu
t
2
]
-
. The analogous ferrocene complex
[Fe(η
5
-P
2
SbC
2
Bu
t
2
)(η
5
-C
5
Me
5
)] (crystal
structure) was synthesized by treating a 1∶1 mixture of
[P
2
SbC
2
Bu
t
2
]
-
and Li(C
5
Me
5
) with half an equivalent of
FeCl
2
. Treatment of
[M(η
5
-P
2
SbC
2
Bu
t
2
)(η
5
-C
5
Me
5
)]
(M = Ru or Fe) with [W(CO)
5
(thf)]
(thf = tetrahydrofuran) formed the secondary co-ordination
complexes
[M(η
5
-P
2
SbC
2
Bu
t
2
)(η
5
-C
5
Me
5
){W(CO)
5
}] (M = Ru or Fe) in which the
W(CO)
5
fragment is η
1
ligated to the
phosphorus centre adjacent to the ring antimony centre. A
diphosphastibolyl-bridged cationic triple-decker complex
[(η
5
-C
5
Me
5
)Ru(µ-η
5
:
η
5
-P
2
SbC
2
Bu
t
2
)Ru(η
5
-C
5
Me
5
)][PF
6
] was the product of the reaction of
[P
2
SbC
2
Bu
t
2
]
-
with 2 equivalents of
[Ru(η
5
-C
5
Me
5
)(MeCN)
3
]
[PF
6
].
Sb interaction in the other isomer restricts its fluxionality in
solution. The reaction of
[P
2
SbC
2
Bu
t
2
]
-
with FeCl
2
yielded only one isomer of the
heteroferrocene complex
[Fe(η
5
-P
2
SbC
2
Bu
t
2
)
2
] which is also non-fluxional in solution and has a
similar oxidation potential to that of ferrocene itself. The
heteroruthenocene complexes
[Ru(η
5
-P
2
SbC
2
Bu
t
2
)(η
5
-C
5
R
5
)]
(R = H or Me) were prepared by treating
[Ru(η
5
-C
5
R
5
)(MeCN)
3
]
[PF
6
] (R = H or Me) with
[P
2
SbC
2
Bu
t
2
]
-
. The analogous ferrocene complex
[Fe(η
5
-P
2
SbC
2
Bu
t
2
)(η
5
-C
5
Me
5
)] (crystal
structure) was synthesized by treating a 1∶1 mixture of
[P
2
SbC
2
Bu
t
2
]
-
and Li(C
5
Me
5
) with half an equivalent of
FeCl
2
. Treatment of
[M(η
5
-P
2
SbC
2
Bu
t
2
)(η
5
-C
5
Me
5
)]
(M = Ru or Fe) with [W(CO)
5
(thf)]
(thf = tetrahydrofuran) formed the secondary co-ordination
complexes
[M(η
5
-P
2
SbC
2
Bu
t
2
)(η
5
-C
5
Me
5
){W(CO)
5
}] (M = Ru or Fe) in which the
W(CO)
5
fragment is η
1
ligated to the
phosphorus centre adjacent to the ring antimony centre. A
diphosphastibolyl-bridged cationic triple-decker complex
[(η
5
-C
5
Me
5
)Ru(µ-η
5
:
η
5
-P
2
SbC
2
Bu
t
2
)Ru(η
5
-C
5
Me
5
)][PF
6
] was the product of the reaction of
[P
2
SbC
2
Bu
t
2
]
-
with 2 equivalents of
[Ru(η
5
-C
5
Me
5
)(MeCN)
3
]
[PF
6
].
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