Reactions of co-ordinated ligands. Part 22. The reactivity of bis-(ethylene)(η5-indenyl)rhodium in displacement reactions with olefins, dienes, and acetylenes; crystal structure of η5-indenyl{l–2 :3–4-η4–[6-endo-propen-2-yl-1,2,3,4-tetrakis(trifluoromethyl)cyclohexa-l,3-diene]}rhodium formed in a cy

doi:10.1039/DT9800000962

Paper

Reactions of co-ordinated ligands. Part 22. The reactivity of bis-(ethylene)(η5-indenyl)rhodium in displacement reactions with olefins, dienes, and acetylenes; crystal structure of η5-indenyl{l–2 :3–4-η4–[6-endo-propen-2-yl-1,2,3,4-tetrakis(trifluoromethyl)cyclohexa-l,3-diene]}rhodium formed in a cy

Published 1980 · Peter Caddy, Michael J. Green, E. O'Brien

Journal of The Chemical Society-dalton Transactions

UNKNOWN SJR score

23

Citations

0

Influential Citations

Full textSemantic Scholar

Abstract

In contrast to the η5-cyclopentadienyl analogue, both of the ethylenes in the compound bis(ethylene)(η5-indenyl)-rhodium are readily displaced by isoprene, cyclo-octatetraene, trans-penta-1,3-diene, trans,trans-hexa-2,4-diene, methylenecyclopropane, or acrylonitrile to afford respectively η5-isoprene-, l–2 : 5–6-η4cyclo-octatetraene-,η4-trans-penta-1,3-diene-, η4-trans,trans-hexa-2,4-diene-, bis(methylenecyclopropane)-, or bis(acrylonitrile)-(η5-indenyl)rhodium. Reaction (room temperature) of hexafluorobut-2-yne with η5-indenyl(η5-isoprene)-rhodium leads to a cyclo-cotrimerisation reaction and the formation of η5-indenyl{l–2: 3–4η4-[6-endo-propen- 2-yl-1,2,3,4-tetrakis(trifluoromethyl)cyclohexa-l,3-diene]}rhodium, the structure in the solid state being established by a single-crystal X-ray diffraction study. Crystals are orthorhombic, space group Pbca(no. 61), with eight molecules in a cell of dimensions a= 16.962(3), b= 29.618(5), and c= 8.596(4)A. The 1,3-diene part of the C6 ring is planar, and is η4-bonded to the rhodium atom, but the two carbon atoms originating from the isoprene bend away from the metal to produce a fold in the C6 ring at a dihedral angle of ca. 132°. The propenyl substituent lies on the same side of the C6 ring as the metal, i.e. is in an endo configuration. An 18-electron configuration for the rhodium is achieved by η5-attachment of the indenyl group, but two of these five carbon atoms are less strongly bonded than the other three. A similar reaction of hexafluorobut-2-yne with η5-indenyl(η4-trans-penta-1,3-diene)rhodium affords related isomeric complexes. A cyclo-cotrimerisation reaction has also been observed between hexafluorobut-2-yne and a co-ordinated ethylene of bis(ethylene)(η5-indenyl)rhodium. Related reactions between 3,3-dimethylbut-1-yne and bis(ethylene)(η5-indenyl)rhodium or bis(acrylonitrile)-(η5-indenyl)rhodium afford respectively [η4-1,4-bis(t-butyl)cyclohexa-1,3-diene]- and [η4-5 cyano-1,4-bis(t-butyl)cyclohexa-l,3-diene]-η5-indenylrhodium. In all of these reactions competitive cyclotrimerisation of the acetylenes occurs to give arenes. The mechanisms of these reactions are discussed.

Study Snapshot

Bis(ethylene)(5-indenyl)-rhodium is highly reactive and can be readily displaced by isoprene, cyclo-octatetraene, trans-penta-1,3-diene, methylenecyclopropane, or acrylon

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

Sign up to use Study Snapshot

Consensus is limited without an account. Create an account or sign in to get more searches and use the Study Snapshot.

Create an account

Paper

Sign up to use Study Snapshot

References

Citations

Indenyl complexes of Group 9 metals: Synthetic and catalytic chemistry

Indenyl complexes of Group 9 metals show high performance in catalytic processes, but their synthetic methods require significant improvements.

Indenylmetal Catalysis in Organic Synthesis.

Indenylmetal complexes show potential for organic synthesis due to their unique properties and reactivity compared to cyclopentadienyl analogues.

Symmetry Breaking in NMR Spectroscopy: The Elucidation of Hidden Molecular Rearrangement Processes

Judicious symmetry breaking in NMR spectroscopy can reveal hidden molecular rearrangement processes, revealing their kinetics and energetics in organic, inorganic, and organometallic chemistry.

Rhodium dinaphthocyclooctatetraene complexes: synthesis, characterization and catalytic activity in [5+2] cycloadditions.

Rhodium dinaphthocyclooctatetraene complexes show excellent catalytic activity in [5+2] cycloadditions of vinylcyclopropanes and -systems with high functional group compatibility.

Photocatalytic properties of new cyclopentadienyl and indenyl rhodium(I) carbonyl complexes with water-soluble 1,3,5-triaza-7-phosphaadamantane (PTA) and tris(2-cyanoethyl)phosphine

New rhodium(I) complexes with water-soluble phosphines show promising photocatalytic properties for dehydrogenation of propan-2-ol, octane, and cyclooctane under photoassisted conditions.

Preparation and synthetic applications of alkene complexes of group 9 transition metals in [2+2+2] cycloaddition reactions.

Group 9 metal-alkene complexes are widely used as catalysts and precursor molecules for facile generation of catalytically active metal species in [2+2+2] cycloaddition reactions.

Synthesis and structure of indenyl rhodium(I) complexes containing unsaturated phosphines: catalyst precursors for alkene hydroboration.

Indenyl rhodium(I) complexes with unsaturated phosphines can catalyze the hydroboration of vinylarenes and internal hydroboration of diphenylvinylphosphine.

Cyclotrimerization reactions catalyzed by rRhodium(I) half-sandwich complexes: A mechanistic density functional study

The mechanism of rRhodium(I) half-sandwich complexes in cycloadditions of acetylene to benzene and acetylene and acetonitrile to 2-methylpyridine involves the formation of a coordinatively uns