Aqueous organometallic chemistry: The mechanism of catalytic hydrogenations with chlorotris(1,3,5-triaza-7-phosphaadamantane) rhodium(I)

Ferenc Joó, L. Nadasdi, A. Bényei, Donald J. Darensbourg

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67 Citations (Scopus)

Abstract

The water-soluble phosphine complex of Rh(I), RhCl(PTA)3 (1) was shown to be an active catalyst for the hydrogenation of various olefinic and oxo-acids, as well as of allyl alcohol and 4-sulfostyrene in aqueous solution under mild conditions. Detailed kinetic investigations were carried out with crotonic acid and allyl alcohol as substrates. The rate of hydrogenation of both compounds showed a sharp maximum as a function of pH at 4.7. Hydrogenation of itaconic, crotonic and α-acetamidocinnamic acid in D2O led to 45-100% deuteration of the products with 25-100% stereoselectivity towards the α-carbon atom. These results, together with those of pH-static hydrogenation of complex 1, suggest that water strongly assists the dehydrochlorination of 1 to yield the catalytically active monohydrido species HRh(PTA)3 (2). Nevertheless, depending on the substrate and the pH of the solution the dihydridic pathway may remain partially operative.

Original languageEnglish
Pages (from-to)45-50
Number of pages6
JournalJournal of Organometallic Chemistry
Volume512
Issue number1-2
Publication statusPublished - Apr 19 1996

Fingerprint

Rhodium
Hydrogenation
Organometallics
rhodium
hydrogenation
chemistry
phosphine
acids
Acids
alcohols
Alcohols
Keto Acids
Stereoselectivity
Water
Substrates
phosphines
water
Carbon
aqueous solutions
catalysts

Keywords

  • Hydrogenation
  • Phosphines
  • Rhodium

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Aqueous organometallic chemistry : The mechanism of catalytic hydrogenations with chlorotris(1,3,5-triaza-7-phosphaadamantane) rhodium(I). / Joó, Ferenc; Nadasdi, L.; Bényei, A.; Darensbourg, Donald J.

In: Journal of Organometallic Chemistry, Vol. 512, No. 1-2, 19.04.1996, p. 45-50.

Research output: Contribution to journalArticle

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