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Induction of planar chirality in formation of (?(5):?(1)-1-(1-cyclohexyl-2-(diphenylphosphino)ethyl)indenyl)-carbonylrhodium and (?(5):?(1)-1-(2-phenyl-2-(diphenylphosphino)ethyl)indenyl)carbonylrhodium

Induction of planar chirality in formation of (?(5):?(1)-1-(1-cyclohexyl-2-(diphenylphosphino)ethyl)indenyl)-carbonylrhodium and (?(5):?(1)-1-(2-phenyl-2-(diphenylphosphino)ethyl)indenyl)carbonylrhodium
Induction of planar chirality in formation of (?(5):?(1)-1-(1-cyclohexyl-2-(diphenylphosphino)ethyl)indenyl)-carbonylrhodium and (?(5):?(1)-1-(2-phenyl-2-(diphenylphosphino)ethyl)indenyl)carbonylrhodium
The enantiopure bidentate indenyl-phosphine ligands (1S)-[2-(3H-inden-1-yl)-1-phenylethyl] diphenylphosphine (9) and [(2R)-2-cyclohexyl-2-(3H-inden-1-yl)ethyl]diphenylphosphine (18) were synthesized in 20% yield and three steps from (R)-styrene oxide and in 61% yield and four steps from vinylcyclohexane, respectively. In both cases ring opening of a spirocyclopropane-1,1'-indene with potassium diphenylphosphide was a key step. Addition of the lithium salts of 9 and 18 to [Rh(? -Cl)(CO)(2)](2) gave (?(5):?(1)-indenyl-CH2CH(Ph)PPh2)RhCO and (?(5):?(1)-indenyl-CH(Cy)CH2PPh2)RhCO as 75:25 and 78:22 mixtures of diastereoisomers, from which the major complexes were readily obtained by crystallization. The chiral centers in the linking chain ? and ? to the indenyl ring had thus induced good planar chirality of the complexed indenyl moiety. Both complexes were characterized by X-ray crystallography.
cyclopentadienyl ligand pcp, transition-metal complexes, crystal-structure, ruthenium complexes, molecular-structures, bidentateligands, zirconium, rhodium, zirconocene, dichlorides
0276-7333
4574-4583
Brookings, Daniel C.
4f4c6f64-7a5e-485c-b5f1-a779c6d13610
Harrison, Stephen A.
f02b6464-d45b-41e3-b2c0-6ccc606d702f
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Crombie, Barry
cebea046-2df3-4f17-bac8-39cc52c06555
Jones, Ray V.H.
c8ffd5a0-7a93-4de5-9164-fb6e3d948a36
Brookings, Daniel C.
4f4c6f64-7a5e-485c-b5f1-a779c6d13610
Harrison, Stephen A.
f02b6464-d45b-41e3-b2c0-6ccc606d702f
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Crombie, Barry
cebea046-2df3-4f17-bac8-39cc52c06555
Jones, Ray V.H.
c8ffd5a0-7a93-4de5-9164-fb6e3d948a36

Brookings, Daniel C., Harrison, Stephen A., Whitby, Richard J., Crombie, Barry and Jones, Ray V.H. (2001) Induction of planar chirality in formation of (?(5):?(1)-1-(1-cyclohexyl-2-(diphenylphosphino)ethyl)indenyl)-carbonylrhodium and (?(5):?(1)-1-(2-phenyl-2-(diphenylphosphino)ethyl)indenyl)carbonylrhodium. Organometallics, 20 (22), 4574-4583. (doi:10.1021/om010367s).

Record type: Article

Abstract

The enantiopure bidentate indenyl-phosphine ligands (1S)-[2-(3H-inden-1-yl)-1-phenylethyl] diphenylphosphine (9) and [(2R)-2-cyclohexyl-2-(3H-inden-1-yl)ethyl]diphenylphosphine (18) were synthesized in 20% yield and three steps from (R)-styrene oxide and in 61% yield and four steps from vinylcyclohexane, respectively. In both cases ring opening of a spirocyclopropane-1,1'-indene with potassium diphenylphosphide was a key step. Addition of the lithium salts of 9 and 18 to [Rh(? -Cl)(CO)(2)](2) gave (?(5):?(1)-indenyl-CH2CH(Ph)PPh2)RhCO and (?(5):?(1)-indenyl-CH(Cy)CH2PPh2)RhCO as 75:25 and 78:22 mixtures of diastereoisomers, from which the major complexes were readily obtained by crystallization. The chiral centers in the linking chain ? and ? to the indenyl ring had thus induced good planar chirality of the complexed indenyl moiety. Both complexes were characterized by X-ray crystallography.

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More information

Published date: 29 October 2001
Keywords: cyclopentadienyl ligand pcp, transition-metal complexes, crystal-structure, ruthenium complexes, molecular-structures, bidentateligands, zirconium, rhodium, zirconocene, dichlorides

Identifiers

Local EPrints ID: 19429
URI: http://eprints.soton.ac.uk/id/eprint/19429
ISSN: 0276-7333
PURE UUID: ed46f877-836e-4f2e-bf9c-28af828d7cea
ORCID for Richard J. Whitby: ORCID iD orcid.org/0000-0002-9891-5502

Catalogue record

Date deposited: 14 Feb 2006
Last modified: 08 Oct 2019 00:57

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