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Formation of 18e − and 16e − Acyl( η 3 ‐cyclooctenyl)rhodium(III) Complexes in the Reaction of Cationic (Cycloocta‐1,5‐diene)rhodium(I) Compounds with 2‐(Diphenylphosphino)benzaldehyde
Author(s) -
El Mail Rachad,
Garralda María A.,
Hernández Ricardo,
Ibarlucea Lourdes,
Pinilla Elena,
Torres M. Rosario
Publication year - 2002
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/1522-2675(200205)85:5<1485::aid-hlca1485>3.0.co;2-a
Subject(s) - rhodium , chemistry , cationic polymerization , diene , aldehyde , medicinal chemistry , oxidative addition , benzaldehyde , stereochemistry , allylic rearrangement , hydroformylation , molecule , crystal structure , catalysis , organic chemistry , natural rubber
Abstract 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‐ η )cyclooct‐2‐en‐1‐yl ( η 3 ‐C 8 H 13 ) formation, and the coordination of a second pCHO molecule as (phosphino‐ κP )aldehyde‐ κO (σ‐coordination) chelate to give the 18e − acyl(allyl)rhodium(III) species [Rh( η 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 − acyl[(1,2,3‐ η )‐cyclooct‐2‐en‐1‐yl]rhodium(III) species [Rh( η 3 ‐C 8 H 13 )(pCO)(PR 3 )]ClO 4 7 – 10 . The (1,2,3‐ η )‐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).