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
ae30426e-d5ac-4502-8b98-0a7d785773ba
2002
Harrison, Stephen Anthony
ae30426e-d5ac-4502-8b98-0a7d785773ba
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
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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: 16 Mar 2024 19:49
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Author:
Stephen Anthony Harrison
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