NMR study of intermediates in the bulky diphosphite modified rhodium catalysed hydroformylation

The stoichiometric hydroformylation reaction of allyldiphenylphosphine with RhH(CO) 2( 2) ( 2 is a bulky diphosphite) was studied using 1H and 31P NMR spectroscopy. Reaction of equimolar amounts in benzene resulted in the formation of RhH(CO)(CH 2=CHCH 2PPh 2)( 2) in which all three phosphorus ligan...

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Bibliographic Details
Published inJournal of organometallic chemistry Vol. 535; no. 1; pp. 201 - 207
Main Authors van Rooy, Annemiek, Kamer, Paul C.J., van Leeuwen, Piet W.N.M.
Format Journal Article
LanguageEnglish
Published Elsevier B.V 15.05.1997
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Summary:The stoichiometric hydroformylation reaction of allyldiphenylphosphine with RhH(CO) 2( 2) ( 2 is a bulky diphosphite) was studied using 1H and 31P NMR spectroscopy. Reaction of equimolar amounts in benzene resulted in the formation of RhH(CO)(CH 2=CHCH 2PPh 2)( 2) in which all three phosphorus ligands are coordinated equatorially ( 4). When 4 was heated, hydride migration occurred leading to two products. Migration to the terminal carbon gave 5, Rh(CO)(PPh 2CH 2CH 2CH 2)( 2). Migration of the hydride to the internal carbon atom was rapidly followed by CO insertion, resulting in the acyl compound 6, containing a five-membered rhodacycle. Complex 6 did not undergo reaction with H 2. Reaction of 5 with CO reversibly yielded acyl complex 7, containing a six-membered rhodacycle. Hydrogenation of 5 yielded 8, the diphenylpropylphosphine analogue of 4.
ISSN:0022-328X
1872-8561
DOI:10.1016/S0022-328X(97)00027-2