102724-33-4Relevant academic research and scientific papers
Novel Basic Ligands for the Homogeneous Catalytic Methanol Carbonylation, VI. The Complex Chemistry of Multidentate (Tetrahydrofurfuryl)phosphanes and their Influence on the Selectivity and Conversion for the Synthesis of Ethanol from Methanol.
Lindner, Ekkehard,Mayer, Hermann August,Wegner, Peter
, p. 2616 - 2630 (2007/10/02)
The P,O ligands Ph2PCH2C4H7O (2) and PhP(CH2C4H7O)2 (3) react with (OC)5MTHF (1a,b) a), W (b)> to give the pentacarbonylmetal complexes 4b and 5a, b, respectively .Irradiation of 4b, 5a, b and the already known 4a in ether affords the kinetic unstable tetracarbonylmetal complexes (OC)4MPPh2CH2C4H7O (6a, b) and (OC)4MPPh(CH2C4H7O)2 (7a, b) with a bidentate function of 2, 3 in each case via phosphorus and oxygen.With CO the reactions are reversible without separation of 2, 3 from the core of the complex .From Mo(CO)6 and 2 trans-(OC)4Mo(PPh2CH2C4H7O)2 (trans-8a) is formed which is rearranged to cis-8a via an opening and closing mechanism with participation of 2 and the labile Mo-O bond .The scission of the W-O bonds in 6b, 7b succeeds also with P(OMe)3 with formation of (OC)4WPPh2CH2C4H7O (9b) and (OC)4WPPh(CH2C4H7O)2 (10b) .The different bonding conditions in 4-7 result from the IR, 31P(1H), 13C(1H), and 1H NMR spectra.The influence of 2 and 3 on the homologation of methanol to ethanol was investigated using cobalt as a component of the catalyst and iodine as a promotor.Dependent on the ratio of the synthesis gas, with 2 and equal catalyst composition in good selectivity either ethanol or methyl acetate is formed with conversions of 50 to 70percent.The catalyst combination survives several cycles intact.
