Abstract

Trivalent phosphorus compounds are promoters for methyl formate homologation to ethanol and ethyl formate catalyzed by ruthenium compounds in the presence of iodide at 220°C and 27 MPa of synthesis gas. Under these conditions the phosphines are quaternized, but decomposition of phosphonium salts occurs during the reaction. Promotion is also observed for methyltriphenyl-phosphonium bromide and triphenylphosphine sulfide, but benzyltrimethyl-ammonium bromide, triphenylarsine, and triphenylantimony are not effective. The major ruthenium species present is Ru(CO) 3I 3 - but with triphenylantimony a trimethylantimony complex, Ru(CO) 2(Sb(CH 3) 3) 2I 2, can be isolated in high yield.

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