Heteroatom-substituted secondary phosphine oxides (HASPOs) as decomposition products and preligands in rhodium-catalysed hydroformylation

Abstract

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.