Berit Bartik

Aqueous phase rhodium hydroformylation of octene-1 with trisulfonated tris (ω-phenyl)alkylphosphines and trisulfonated triphenyl phosphine. Reaction selectivity as an indication of rhodium-phosphine complex chemistry

Abstract The electron donating, water soluble phosphines, P[ (CH 2 ) x C 6 H 4 - p -SO 3 3Na] 3 , x =1, 2, 3, 6, are used to generate aqueous rhodium catalysts for the hydroformylation of octene-1. At low L/ Rh ratios conversion generally increases with increasing number of methylene groups. At high L/ Rh ratios the catalytic activity decreases. For comparison data are given for P (C 6 H 4 - m -SO 3 Na) 3 , TPPTS, as well. The new complexes, Rh (acac) (CO)L, where L=P[ (CH 2 ) x C 6 H 4 - p -SO 3 Na] 3 , x =1, 2, 3, 6, and HRh (CO)L 3 where L=P[(CH 2 ) 2 C 6 H 4 - p -SO 3 Na] 3 , are described. The latter compound, HRh (CO)L 3 , appears to oxidatively add water to yield [H 2 Rh(CO)L 3 ] + .

Surface active phosphines for catalysis under two-phase reaction conditions. P(menthyl) [(CH2)8C6H4-p-SO3Na]2 and the hydroformylation of styrene

Abstract The novel optically active phosphine, bis(8-phenyloctyl) (Menth) phosphine, (Menth = 1R,3R,4S( - )menthyl) is synthesized and sulfonated under mild conditions to yield the corresponding sulfonated phosphine, disodium bis-(8-(para-sulfonatophenyl)octyl) (Menth) phosphine. The water soluble phosphine is used to generate an aqueous-methanol rhodium catalyst for the hydroformylation of styrene. The catalyst shows high catalytic activity, but virtually no optical induction. Normal to branch ratios for the hydroformylation of styrene are in the range 0.35 to 0.5. The catalytic data with TPPTS is given for comparison. TPPTS yields catalysts that are less active under two phase reaction conditions and slightly less selective for formation of 2-phenylpropanal.

Synthesis and characterization of Na5[Co(CO)3(P{(CH2)nC6H4-P-SO3}3)2], n = 1, 2, 3, and 6. Novel zwitterion

Abstract The electron donating water soluble phosphines, P{(CH 2 ) n C 6 H 4 - p -SO 3 Na} 3 , n = 1, 2, 3 and 6, react rapidly with Co 2 (CO) 8 under two phase reaction conditions to yield the disproportionation products, [Co(CO) 3 (P{(CH 2 ) n C 6 H 4 - p -SO 3 Na 3 } 2 ] [Co(CO) 4 ]. Selective precipitation yields the formally zwitterionic complex anions as the sodium salt, [Co(CO) 3 (P{(CH 2 ) n C 6 H 4 - p -SO 3 } 3 ) 2 ] 5− . The anions can be used as precursors to water soluble cobalt hydroformylation catalysts under two phase and supported aqueous phase conditions. The tendency to form alcohol products is low with these complexes. The behavior of the catalysts is consistent with an active species that remains water soluble during the reaction and is not leached into the nonaqueous phase.

Effect of water on tributylphosphine modified cobalt carbonyl catalysts for the hydroformylation of olefins

Abstract Water is seen to have a dramatic effect on the alcohol/aldehyde distribution in the P (nBu) 3 modified cobalt carbonyl catalyzed hydroformylation of 1-octene. In particular the rate of alcohol synthesis is greater in the presence of water. Under the conditions used the effect is first noticable at 5 vol.-% water. At high conversion the effect is still observed but is not as significant.

Phosphorus-31 NMR spin lattice relaxation times as an indirect probe of adsorbed water in supported aqueous phase catalysts

Abstract Phosphorus-31 spin lattice relaxation times, T1s, for SAP hydroformylation catalysts derived from HRh (CO) (TPPTS)3 and TPPTS (TPPTS = trisulfonated triphenyl phosphine trisodium salt) are consistent with a liquid-like character for the supported aqueous phase. Ale T1 for solid TPPTS is 1150 s while for TPPTS in a supported aqueous phase T1 varies from 220 to 4.9 s. A T1 of 4.9 s is close to the value obtained for TPPTS in solution and is observed at a H2O/P ratio of 24.9. At this level of water content previously reported SAP catalysts have shown maximum catalytic activity for the hydroformylation of olefins.

New Water Soluble Phosphines for Organometallic Chemistry and Catalysis in the Aqueous Phase

The fact that water soluble phosphines may also be surface active was first noted by Wilkinson et al. in their study of the hydroformylation of 1-hexene with rhodium complexes of P(C6H5)2(C6H4SO3Na), TPPMS.1 Specifically it was stated that aqueous solutions of TPPMS have a tendency to form emulsions that separated slowly. While TPPMS has definite hydrophobic and hydrophilic regions it does not have the general shape of micelle forming surfactants. Specifically it is more disk shaped than rod-like.