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Heteroatom‐Substituted Secondary Phosphine Oxides (HASPOs) as Decomposition Products and Preligands in Rhodium‐Catalysed Hydroformylation
Author(s) -
Christiansen Andrea,
Selent Detlef,
Spannenberg Anke,
Köckerling Martin,
Reinke Helmut,
Baumann Wolfgang,
Jiao Haijun,
Franke Robert,
Börner Armin
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002823
Subject(s) - hydroformylation , rhodium , chemistry , phosphine , heteroatom , catalysis , organic chemistry , phosphine oxide , phosphonate , medicinal chemistry , ring (chemistry)
O , O ′‐3,3′‐Di‐ tert ‐butyl‐5,5′‐dimethoxy‐1,1′‐biphenyl‐2,2′‐diyl phosphonate ( 1 ) is the hydrolysis product of several mono‐ and bis‐phosphites used as ligands in industrial hydroformylation and other catalytic reactions. As a result of a tautomeric equilibrium, this pentavalent heteroatom‐substituted phosphine oxide (HASPO) can rearrange to the corresponding trivalent phosphorus compound. The latter is able to react with typical rhodium‐containing precursors frequently used for the generation of catalysts. The resulting species were characterised by NMR spectroscopy and X‐ray structure analysis. Proof is given that a rhodium complex of 1 forms an active hydroformylation catalyst. Moreover, 1 can add to aldehydes, which are generated as products in the hydroformylation. Thus a broad range of subsequent reactions can be associated with the degradation of the original phosphite ligands, which has a strong influence on the overall outcome of the hydroformylation reaction.