Syntheses and characterization of iridium and rhodium ethylene complexes containing a doubly linked cyclopentadienyl ligand
A one step reaction to a doubly linked Cp ligand and its corresponding iridium and rhodium ethylene complexes. The dimerization of 6,6-dimethylfulvene with Ni(cod) 2 yields the 4,4,8,8-tetramethyl-3a,4,7a,8-tetrahydro- s-indacene isomer ( 1a). Heating a solution of 1a converts it to the 1,4,5,8 ( 1b...
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| Published in: | Inorganica Chimica Acta Vol. 362; no. 2; pp. 389 - 394 |
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| Main Authors: | , , , , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
Elsevier B.V
20-01-2009
|
| Subjects: | |
| Online Access: | Get full text |
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| Summary: | A one step reaction to a doubly linked Cp ligand and its corresponding iridium and rhodium ethylene complexes.
The dimerization of 6,6-dimethylfulvene with Ni(cod)
2 yields the 4,4,8,8-tetramethyl-3a,4,7a,8-tetrahydro-
s-indacene isomer (
1a). Heating a solution of
1a converts it to the 1,4,5,8 (
1b) and 1,4,7,8 (
1c) tetrahydro-
s-indacene isomers. The activation energy for the isomerization is 23(1)
kcal/mol.
1b and
1c can be deprotonated with
n-BuLi and the reaction of the dianion with [ClIr(C
2H
4)
2]
2 gives two isomers,
cis-[(η
5-C
5H
3)(CMe
2)Ir(C
2H
4)
2]
2 (
cis-
2) and
trans-[(η
5-C
5H
3)(CMe
2)Ir(C
2H
4)
2]
2 (
trans-
2). Reaction of
1b and
1c with RhCl
3
·
xH
2O in refluxing methanol yields a red-orange solid, which was consistent with the empirical formula, [(C
5H
3)(CMe
2)RhCl
2]
n
(
3). Reaction of
3 with C
2H
4 in a Na
2CO
3/ethanol mixture afforded
cis-[(η
5-C
5H
3)(CMe
2)Rh(C
2H
4)
2]
2 in 5% yield. |
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| ISSN: | 0020-1693 1873-3255 |
| DOI: | 10.1016/j.ica.2008.04.025 |