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Issue 1, 2009
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Stereoelectronic effects in a homologous series of bidentate cyclic phosphines. A clear correlation of hydroformylation catalyst activity with ring size

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Abstract

The homologous series of diphosphines (CH2)n−1P(CH2)3P(CH2)n−1 where n = 5 (L5), 6 (L6), or 7 (L7) have been synthesized from the corresponding PhP(CH2)n−1. Treatment of [PtCl2(cod)] with L5–7 gave the 6-membered chelates cis-[PtCl2(L5–7)], the crystal structures for which reveal that L5–7 have very similar steric bulk and bite angles. Treatment of [Rh2Cl2(CO)4] with L5–7 gave the binuclear trans-[Rh2Cl2(CO)2(μ-L5–7)2] with syn and anti orientations of the CO and Cl ligands suggested by the 31P NMR spectra and the crystal structures of syn–trans-[Rh2Cl2(CO)2(μ-L5)2] and anti–trans-[Rh2Cl2(CO)2(μ-L7)2]. The ν(CO) values for trans-[Rh2Cl2(CO)2(μ-L5–7)2] indicate that the donor strength increases in the order L5 < L6 < L7. A study of rhodium-catalysed hydroformylation of 1-octene using diphosphines L5–7 is described. The catalyst activity decreases with increasing phosphacycle ring size: L5 > L6 > L7.

Graphical abstract: Stereoelectronic effects in a homologous series of bidentate cyclic phosphines. A clear correlation of hydroformylation catalyst activity with ring size

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Supplementary files

Article information


Submitted
29 Aug 2008
Accepted
14 Oct 2008
First published
25 Nov 2008

Dalton Trans., 2009, 202-209
Article type
Paper

Stereoelectronic effects in a homologous series of bidentate cyclic phosphines. A clear correlation of hydroformylation catalyst activity with ring size

M. F. Haddow, A. J. Middleton, A. G. Orpen, P. G. Pringle and R. Papp, Dalton Trans., 2009, 202
DOI: 10.1039/B815056G

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