Formation of 18e− and 16e− Acyl(η3-cyclooctenyl)rhodium(III) Complexes in the Reaction of Cationic (Cycloocta-1,5-diene)rhodium(I) Compounds with 2-(Diphenylphosphino)benzaldehyde
✍ Scribed by Rachad El Mail; María A. Garralda; Ricardo Hernández; Lourdes Ibarlucea; Elena Pinilla; M. Rosario Torres
- Publisher
- John Wiley and Sons
- Year
- 2002
- Tongue
- German
- Weight
- 137 KB
- Volume
- 85
- Category
- Article
- ISSN
- 0018-019X
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✦ Synopsis
The reaction of cationic diolefinic rhodium(I) complexes with 2-(diphenylphosphino)benzaldehyde (pCHO) was studied. [Rh(cod) 2 ]ClO 4 (cod cycloocta-1,5-diene) reacted with pCHO to undergo the oxidative addition of one pCHO with (1,2,3-h)cyclooct-2-en-1-yl (h 3 -C 8 H 13 ) formation, and the coordination of a second pCHO molecule as (phosphino-kP)aldehyde-kO(s-coordination) chelate to give the 18e À acyl(allyl)rhodium(III) species [Rh(h 3 -C 8 H 13 )(pCO)(pCHO)]ClO 4 (see 1). Complex 1 reacted with [Rh(cod)(PR 3 ) 2 ]ClO 4 (R aryl) derivatives 3 ± 6 to give stable pentacoordinated 16e À acyl[(1,2,3-h)-cyclooct-2-en-1-yl]rhodium(III) species [Rh(h 3 -C 8 H 13 )(pCO)(PR 3 )]ClO 4 7 ± 10. The (1,2,3-h)-cyclooct-2-en-1-yl complexes contain cis-positioned P-atoms and were fully characterized by NMR, and the molecular structure of 1 was determined by X-ray crystal diffraction. The rhodium(III) complex 1 catalyzed the hydroformylation of hex-1-ene and produced 98% of aldehydes (n/iso 2.6).