Promotion by phosphorus compounds of ruthenium-catalyzed methyl formate homologation

Jerome B. Keister; Robert Gentile

doi:10.1016/S0022-328X(00)89023-3

Promotion by phosphorus compounds of ruthenium-catalyzed methyl formate homologation

Jerome B. Keister
, Robert Gentile

Chemistry

ExxonMobil

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

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)₃I₃^- but with triphenylantimony a trimethylantimony complex, Ru(CO)₂(Sb(CH₃)₃)₂I₂, can be isolated in high yield.

Original language	English
Pages (from-to)	143-153
Number of pages	11
Journal	Journal of Organometallic Chemistry
Volume	222
Issue number	1
DOIs	https://doi.org/10.1016/S0022-328X(00)89023-3
State	Published - Dec 15 1981

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title = "Promotion by phosphorus compounds of ruthenium-catalyzed methyl formate homologation",

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)3I3- but with triphenylantimony a trimethylantimony complex, Ru(CO)2(Sb(CH3)3)2I2, can be isolated in high yield.",

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AU - Keister, Jerome B.

AU - Gentile, Robert

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N2 - 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)3I3- but with triphenylantimony a trimethylantimony complex, Ru(CO)2(Sb(CH3)3)2I2, can be isolated in high yield.

AB - 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)3I3- but with triphenylantimony a trimethylantimony complex, Ru(CO)2(Sb(CH3)3)2I2, can be isolated in high yield.

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DO - 10.1016/S0022-328X(00)89023-3

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SP - 143

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JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1

ER -

Promotion by phosphorus compounds of ruthenium-catalyzed methyl formate homologation

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