High-pressure NMR studies of the water soluble rhodium hydroformylation system

I. Horváth, Rodney V. Kastrup, Alexis A. Oswald, Edmund J. Mozeleski

Research output: Contribution to journalArticle

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Abstract

Rh(CO)2(acac) reacts with P(m-C6H4SO3Na.H2O)3 (P/Rh > 3.5) in water under CO to give HRh(CO)[P(m-C6H4SO3Na)3]3 (1a), the structure of which is similar to HRh(CO) (PPh3)3 (1b). High pressure NMR spectra of an aqueous solution containing 1a and three molar excess of P(m-C6H4SO3Na)3 does not show the formation of new species up to 200 atm of CO:H2(1:1). In contrast, 1b, in the presence of three molar excess of PPh3, is completely converted to HRh(CO)2(PPh3)2 (2b) under 30 atm CO/H2(1:1) in toluene. The activation energy of the dissociation of P(m-C6H4SO3Na)3 from 1a in water was found to be 30±1 kcal/mol, which is 11±1 kcal/mol higher than the dissociation of PPh3 from 1b in toluene.

Original languageEnglish
Pages (from-to)85-90
Number of pages6
JournalCatalysis Letters
Volume2
Issue number2
DOIs
Publication statusPublished - Mar 1989

Fingerprint

Hydroformylation
Rhodium
Carbon Monoxide
rhodium
Toluene
toluene
Nuclear magnetic resonance
dissociation
nuclear magnetic resonance
Water
water
Activation energy
activation energy
aqueous solutions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Catalysis

Cite this

High-pressure NMR studies of the water soluble rhodium hydroformylation system. / Horváth, I.; Kastrup, Rodney V.; Oswald, Alexis A.; Mozeleski, Edmund J.

In: Catalysis Letters, Vol. 2, No. 2, 03.1989, p. 85-90.

Research output: Contribution to journalArticle

Horváth, I. ; Kastrup, Rodney V. ; Oswald, Alexis A. ; Mozeleski, Edmund J. / High-pressure NMR studies of the water soluble rhodium hydroformylation system. In: Catalysis Letters. 1989 ; Vol. 2, No. 2. pp. 85-90.
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AB - Rh(CO)2(acac) reacts with P(m-C6H4SO3Na.H2O)3 (P/Rh > 3.5) in water under CO to give HRh(CO)[P(m-C6H4SO3Na)3]3 (1a), the structure of which is similar to HRh(CO) (PPh3)3 (1b). High pressure NMR spectra of an aqueous solution containing 1a and three molar excess of P(m-C6H4SO3Na)3 does not show the formation of new species up to 200 atm of CO:H2(1:1). In contrast, 1b, in the presence of three molar excess of PPh3, is completely converted to HRh(CO)2(PPh3)2 (2b) under 30 atm CO/H2(1:1) in toluene. The activation energy of the dissociation of P(m-C6H4SO3Na)3 from 1a in water was found to be 30±1 kcal/mol, which is 11±1 kcal/mol higher than the dissociation of PPh3 from 1b in toluene.

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