Hydridorhodium(I) complexes with amphiphilic polyether phosphines - NMR study and biphasic hydroformylation of 1-octene

作者：Solsona A; Suades J^*; Mathieu R

来源：Journal of Organometallic Chemistry, 2003, 669(1-2): 172-181.

DOI：10.1016/S0022-328X(03)00040-8

• hydridorhodium(I) complexes
• amphiphilic phosphines
• biphasic hydroformylation

The formation of hydridorhodium(I) complexes with the amphiphilic phosphines 4-(R)C6H4(OCH2CH2)(n)PPh2 (R = 2,2,4,4-tetramethylbutyl, n = 1, (n) over bar = 5) was studied by NMR methods and IR spectroscopy. Two approaches were used: (1) the substitution reaction of triphenylphosphine in RhH(CO)(PPh3)(3) by an amphiphilic phosphine and (2) a reaction between the precursor Rh(acac)(CO)(2), syngas and the amphiphilic ligand in hydroformylation reaction conditions. Both approaches show the formation of P-coordinated hydridorhodium(l) complexes, and no relevant chelated (P, O) complexes were recognised. The biphasic rhodium-catalysed hydroformylation of 1-octene with the following water-soluble amphiphilic phosphines was studied: 4-(R)C6H4(OCH2CH2)(n)P(Ph)CH2CH2SO3Na (R = 2,2,4,4-tetramethylbutyl, (n) over bar = 1.4, 5.1, 11.2; R = n-nonyl, (n) over bar = 1.6, 5.6, 11.4), and RP(Ph)CH2CH2SO3Na (R = n -octyl, CH3(OCH2CH2)(2)OCH2CH2). Ligands with a hydrophobic group and a short polyether chain led to the higher conversion. This result is ascribed to the ability of these ligands to increase the metal concentration in the organic phase.

• 出版日期2003-3-3