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Novel chiral cyclopentadienyl metal complexes

Novel chiral cyclopentadienyl metal complexes
Novel chiral cyclopentadienyl metal complexes

The synthesis of the known two-carbon linked chiral indenyl-phosphine ligand (1S)-[2-3H-inden-1-yl)-1-phenylethyl]diphenyl-phosphine 59 has been repeated, and the unexpected rearrangement during the final step of its synthesis, involving the spirocyclic intermediate (R,R)-spiro[2-phenylcyclopropane)-1,1’-indene], has been investigated. The novel two-carbon linked chiral ligand [(2R)-2-cyclohexyl-2-(3H-inden-1-yl)ethyl]-diphenylphosphine 121, has been prepared and its synthesis optimised to provide 61 % yield of enantiopure 121 from commercial vinylcyclohexane. The lithium salt of 121 has been complexed with [Rh(μ-C1)(CO)2]2 to form its rhodium(I) complex 154, with 56 % d.e. induction of planar-chirality. Complexation of 121 with RuC12(PPh3)3 has also been achieved, and the resulting ruthenium(II) complex 147 formed with 60 % d.e. induction of planar-chirality and complete control of metal-centred chirality. Unfortunately initial catalytic trials of the ruthenium(II) complex have proved disappointing. The ruthenium complex has been hydrogenated to the tetrahydroindenyl complex 148.

The novel diphenyl-substituted two-carbon linked ligand rac-[1,2-diphenyl-2-(3H-inden-1-yl)ethyl]diphenyl-phosphine 128 has been prepared and complexed with RuC12(PPh3)3 to form its ruthenium complex 149, with 74 % d.e. induction of planar-chirality. The novel three-carbon linked indene-phosphine ligand rac-[3-cyclohexyl-3-(3H-inden-1-yl)propyl]-diphenyl-phosphine 129 has been prepared in 36 % overall yield from malonic acid and cyclohexane carboxaldehyde via a synthetic route involving the 1,4-addition of indenyl lithium to an α,β-unsaturated ester.

X-ray structures six of the above organometallic complexes have been obtained, as well as five X-ray structures of intermediates formed during the syntheses of their ligands.

University of Southampton
Harrison, Stephen Anthony
Harrison, Stephen Anthony

Harrison, Stephen Anthony (2002) Novel chiral cyclopentadienyl metal complexes. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

The synthesis of the known two-carbon linked chiral indenyl-phosphine ligand (1S)-[2-3H-inden-1-yl)-1-phenylethyl]diphenyl-phosphine 59 has been repeated, and the unexpected rearrangement during the final step of its synthesis, involving the spirocyclic intermediate (R,R)-spiro[2-phenylcyclopropane)-1,1’-indene], has been investigated. The novel two-carbon linked chiral ligand [(2R)-2-cyclohexyl-2-(3H-inden-1-yl)ethyl]-diphenylphosphine 121, has been prepared and its synthesis optimised to provide 61 % yield of enantiopure 121 from commercial vinylcyclohexane. The lithium salt of 121 has been complexed with [Rh(μ-C1)(CO)2]2 to form its rhodium(I) complex 154, with 56 % d.e. induction of planar-chirality. Complexation of 121 with RuC12(PPh3)3 has also been achieved, and the resulting ruthenium(II) complex 147 formed with 60 % d.e. induction of planar-chirality and complete control of metal-centred chirality. Unfortunately initial catalytic trials of the ruthenium(II) complex have proved disappointing. The ruthenium complex has been hydrogenated to the tetrahydroindenyl complex 148.

The novel diphenyl-substituted two-carbon linked ligand rac-[1,2-diphenyl-2-(3H-inden-1-yl)ethyl]diphenyl-phosphine 128 has been prepared and complexed with RuC12(PPh3)3 to form its ruthenium complex 149, with 74 % d.e. induction of planar-chirality. The novel three-carbon linked indene-phosphine ligand rac-[3-cyclohexyl-3-(3H-inden-1-yl)propyl]-diphenyl-phosphine 129 has been prepared in 36 % overall yield from malonic acid and cyclohexane carboxaldehyde via a synthetic route involving the 1,4-addition of indenyl lithium to an α,β-unsaturated ester.

X-ray structures six of the above organometallic complexes have been obtained, as well as five X-ray structures of intermediates formed during the syntheses of their ligands.

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Published date: 2002

Identifiers

Local EPrints ID: 464915
URI: http://eprints.soton.ac.uk/id/eprint/464915
PURE UUID: fde0d081-3aae-4c12-b013-b8a02a079e78

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Date deposited: 05 Jul 2022 00:09
Last modified: 05 Jul 2022 03:32

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Author: Stephen Anthony Harrison

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