Skip to content

Research at St Andrews

Deuterium labelling evidence for a hydride mechanism in the formation of methyl propanoate from carbon monoxide, ethene and methanol catalysed by a palladium complex

Research output: Contribution to journalArticle

DOI

Author(s)

GR Eastham, RP Tooze, M Kilner, DF Foster, David John Cole-Hamilton

School/Research organisations

Abstract

Reaction of ethene with CO in CH3OD in the presence of a catalyst prepared in situ from [Pd(DBPMB)(DBA)] (DBPMB=1,2-bis[(di-tert-butyl)phosphinomethyl] benzene, DBA=dibenzylideneacetone) and methanesulfonic acid under conditions of good gas mixing gives a 1:1 mixture of CH2DCH2CO2Me and CH3CHDCO2Me with no H incorporated into the CH3OD. If the gas mixing is less efficient, the methyl propanoate has 0-5 D atoms incorporated in the ethyl group, CH3OD exchanges to give increasing amounts of CH3OH throughout the reaction and there is a slight increase in the less deuteriated products with reaction time. Significant D incorporation into unreacted ethene is also observed. These results are interpreted in terms of a hydride mechanism with the rates of the individual steps under conditions of good mixing being: reversible H migration to coordinated ethene >CO coordination much greater thanC(2)H(4) exchange >H/D exchange.

Close

Details

Original languageEnglish
Pages (from-to)1613-1617
Number of pages5
JournalJournal of the Chemical Society, Dalton Transactions
DOIs
Publication statusPublished - 2002

    Research areas

  • ALTERNATING COPOLYMERIZATION, METHOXYCARBONYLATION, ETHYLENE

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. Synthesis of pharmaceutical drugs from cardanol derived from cashew nut shell liquid

    Shi, Y., Kamer, P. C. J. & Cole-Hamilton, D. J., 7 Mar 2019, In : Green Chemistry. 21, 5, p. 1043-1053 11 p.

    Research output: Contribution to journalArticle

  2. Periodic table: new version warns of elements that are endangered

    Cole-Hamilton, D., 24 Jan 2019, The Conversation.

    Research output: Contribution to specialist publicationArticle

  3. Employment and Careers of European Chemists (ESEC2)

    Salzer, R., Cole-Hamilton, D., Hrastelj, N. & Vilela, B., 20 Nov 2018, In : Chemistry - A European Journal. 24, 66, p. 17370-17388 19 p.

    Research output: Contribution to journalEditorial

  4. The European Chemical Society (EuChemS)

    Cole-Hamilton, D. J., 14 Aug 2018, In : Chemistry - A European Journal. 24, 46, p. 11811-11820

    Research output: Contribution to journalArticle

  5. Insight into the mechanism of decarbonylation of methanol by ruthenium complexes; a deuterium labelling study

    Lorusso, P., Eastham, G. & Cole-Hamilton, D. J., 15 Jun 2018, In : Dalton Transactions. In press

    Research output: Contribution to journalArticle

Related by journal

Related by journal

  1. Journal of the Chemical Society, Dalton Transactions (Journal)

    David John Cole-Hamilton (Editor)
    20002003

    Activity: Publication peer-review and editorial work typesEditor of research journal

ID: 191554

Top