WATER-SOLUBLE METAL-COMPLEXES AND CATALYSTS .7. NEW EFFICIENT WATER-SOLUBLE CATALYSTS FOR 2-PHASE OLEFIN HYDROFORMYLATION - BINAS-NA, A SUPERLATIVE IN PROPENE HYDROFORMYLATION

The monophosphine imethyl-2,5,6-triphenyl-1-phosphanorboma-2,5-diene ( 1,DMTPPNOR) and the diphosphine 2'-bis(diphenylphosphinomethyl)-1,1'-b inaphthalene (7) were sulfonated by means of oleum. The sulfonation pr oducts 8 (BINAS) and 2 (NORBOS) were purified by extraction-reextracti on and by gel permeation chromatography. While the sodium salt 9 (BINA S-Na) of BINAS (8) was accessible as a mixture of different degrees of sulfonation, the sodium salt of NORBOS (2) was available as an analyt ically clean, completely characterized, triply sulfonated compound, NO RBOS-Na (3). For the synthesis of 2'-bis(diphenylphosphinomethyl)-1,1' -binaphthalene (7), a new method has been used: Commercially available 1-bromo-2-methylnaphthalene (4) was first dimerized by means of magne sium, and then the resulting 2,2'-dimethyl-1,1-'binaphthalene (5) was treated with n-BuLi/TMEDA and chlorodiphenylphosphine. In the 'heterog eneous' (bi-phasic) hydroformylation of propene, the sulfonated ligand s 3 and 9 exhibited very high activities and productivities at low pho sphine/rhodium ratios. Furthermore, phosphine 9 was advantageous in n/ iso ratios of the resulting butyric aldehyde (rhodium catalysis). The new catalyst system Rh-1/BINAS-Na has an apparent activation energy of 10.8 kcal/mol explaining the outstanding performance of this system i n continuous hydroformylation, with the activity data being. 16 (TPPTS ), 90 (BISBIS-Na), 118 (NORBOS-Na), and 178 (BINAS-Na).