Heterocyclic organotellurium compounds as precursors for new organometallic derivatives of rhodium
Abstract
The reaction of the
pentamethylcyclopentadienylrhodium(III) dichloride dimer,
[{Rh(η-C
5
Me
5
)Cl
2
}
2
], with tellurophene in the presence of
Ag(O
3
SCF
3
) afforded the expected
[Rh(η-C
5
Me
5
)(η
5
-C
4
H
4
Te)][O
3
SCF
3
]
2
1
which on reaction with [Co(cp)
2
]
(cp = η-C
5
H
5
) gives a
rhodacyclic material
[Rh(η-C
5
Me
5
){η
5
-C
5
H
4
Rh(η-C
5
Me
5
)}]
2. The reaction of 2 with
[Fe
3
(CO)
12
] gave
[Rh(η-C
5
Me
5
){η
5
-C
4
H
4
Fe(CO)
3
}] 3. The reaction of
[{Rh(η-C
5
Me
5
)Cl
2
}
2
] with dibenzotellurophene, dbt, in the presence of
Ag(O
3
SCF
3
) gives
[Rh(η-C
5
Me
5
)(dbt)][O
3
SCF
3
]
2
4, in which the mode of coordination of dbt
in CDCl
3
solution appears to be η
1
. The
reaction of 4 with [Co(cp)
2
] and
[Fe
3
(CO)
12
] gave a variety of products including
[Rh(η-C
5
Me
5
)(C
12
H
8
)(
η
1
-dbt)] 5, a known dibenzoferrole, 6,
and compound 7 in which the η
1
-dbt of 5
is substituted by CO. Also isolated were the known
[{Fe(η-C
5
Me
5
)(CO)
2
}
2
] 8 and FeTe. The direct reaction of
[{Rh(η-C
5
Me
5
)Cl
2
}
2
] and dbt gave
[Rh(η-C
5
Me
5
)Cl
2
(η
1
-dbt)]. Two complexes of 2-telluraindane were synthesized for
comparison,
[Rh(η-C
5
Me
5
)(C
8
H
8
Te)][O
3
SCF
3
]
2
10 and
[Rh(η-C
5
Me
5
)Cl
2
(C
8
H
8
Te)] 11 the latter showing fluxionality about
co-ordinated tellurium at room temperature. It is suggested that the
magnitude of
J (
125
Te–
103
Rh) has
the potential to differentiate the modes of co-ordination of
heterocyclic tellurium compounds to rhodium. The crystal and molecular
structures have been determined for compounds 5, 7 and
9.
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