Structural evolution of a recoverable rhodium hydrogenation catalyst

Wendy J. Shaw, Yongsheng Chen, John Fulton, John Linehan, Anna Gutowska, Tom Bitterwolf

Research output: Contribution to journal › Article

8 Citations (Scopus)

Abstract

A recoverable, water soluble, hydrogenation catalyst was synthesized by reacting poly-N-isopropylacrylamide containing a terminal amino group (H2N-CH2CH2-S-pNIPAAm) with [Rh(CO)2Cl]2 in organic solvents to form the square planar rhodium complex (Rh(CO)2Cl(H2N-CH2CH2-S-pNIPAAm)). The catalyst-ligand structure was characterized using in situ multinuclear NMR, XAFS and IR spectroscopic methods. Model complexes containing glycine (H2NCH2COOH), cysteamine (H2NCH2CH2SH) and methionine methyl ester (H2NCH(CH2CH2SCH3)COOCH3) ligands were studied to aid in the interpretation of the coordination sphere of the rhodium catalyst. The spectroscopic data revealed a switch in ligation from the amine bound (Rh-NH2-CH2CH2-S-pNIPAAm) to the thioether bound (Rh-S(-CH2CH2NH2)(-pNIPAAm)) rhodium when the complex was dissolved in water. The evolution of the structure of the rhodium complex dissolved in water was followed by XAFS. The structure changed from the expected monomeric complex to form a rhodium cluster of up to four rhodium atoms containing one SRR′ ligand and one CO ligand per rhodium center. No metallic rhodium was observed during this transformation. The rhodium-rhodium interactions were disrupted when an alkene (3-butenol) was added to the aqueous solution. The kinetics of the hydrogenation reaction were measured using a novel high-pressure flow-through NMR system and the catalyst was found to have a TOF of 3000/Rh/h at 25 °C for the hydrogenation of 3-butenol in water.

Original languageEnglish
Pages (from-to)2111-2118
Number of pages8
JournalJournal of Organometallic Chemistry
Volume693
Issue number12
DOIs
Publication statusPublished - Jun 1 2008

Fingerprint

Rhodium
Hydrogenation
rhodium
hydrogenation
catalysts
Catalysts
Carbon Monoxide
Ligands
ligands
Water
water
Nuclear magnetic resonance
cysteamine
Biomolecular Nuclear Magnetic Resonance
Cysteamine
methionine
nuclear magnetic resonance
Alkenes
Sulfides
glycine

Keywords

  • Aqueous rhodium catalysts
  • High pressure NMR
  • Homogeneous catalysis
  • Recoverable catalyst
  • Stimulus sensitive polymers

ASJC Scopus subject areas

  • Chemical Engineering (miscellaneous)
  • Materials Science (miscellaneous)
  • Materials Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Biochemistry

Cite this

Structural evolution of a recoverable rhodium hydrogenation catalyst. / Shaw, Wendy J.; Chen, Yongsheng; Fulton, John; Linehan, John; Gutowska, Anna; Bitterwolf, Tom.

In: Journal of Organometallic Chemistry, Vol. 693, No. 12, 01.06.2008, p. 2111-2118.

Research output: Contribution to journal › Article

Shaw, WJ, Chen, Y, Fulton, J, Linehan, J, Gutowska, A & Bitterwolf, T 2008, 'Structural evolution of a recoverable rhodium hydrogenation catalyst', Journal of Organometallic Chemistry, vol. 693, no. 12, pp. 2111-2118. https://doi.org/10.1016/j.jorganchem.2008.03.011
Shaw WJ, Chen Y, Fulton J, Linehan J, Gutowska A, Bitterwolf T. Structural evolution of a recoverable rhodium hydrogenation catalyst. Journal of Organometallic Chemistry. 2008 Jun 1;693(12):2111-2118. https://doi.org/10.1016/j.jorganchem.2008.03.011
Shaw, Wendy J. ; Chen, Yongsheng ; Fulton, John ; Linehan, John ; Gutowska, Anna ; Bitterwolf, Tom. / Structural evolution of a recoverable rhodium hydrogenation catalyst. In: Journal of Organometallic Chemistry. 2008 ; Vol. 693, No. 12. pp. 2111-2118.
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N2 - A recoverable, water soluble, hydrogenation catalyst was synthesized by reacting poly-N-isopropylacrylamide containing a terminal amino group (H2N-CH2CH2-S-pNIPAAm) with [Rh(CO)2Cl]2 in organic solvents to form the square planar rhodium complex (Rh(CO)2Cl(H2N-CH2CH2-S-pNIPAAm)). The catalyst-ligand structure was characterized using in situ multinuclear NMR, XAFS and IR spectroscopic methods. Model complexes containing glycine (H2NCH2COOH), cysteamine (H2NCH2CH2SH) and methionine methyl ester (H2NCH(CH2CH2SCH3)COOCH3) ligands were studied to aid in the interpretation of the coordination sphere of the rhodium catalyst. The spectroscopic data revealed a switch in ligation from the amine bound (Rh-NH2-CH2CH2-S-pNIPAAm) to the thioether bound (Rh-S(-CH2CH2NH2)(-pNIPAAm)) rhodium when the complex was dissolved in water. The evolution of the structure of the rhodium complex dissolved in water was followed by XAFS. The structure changed from the expected monomeric complex to form a rhodium cluster of up to four rhodium atoms containing one SRR′ ligand and one CO ligand per rhodium center. No metallic rhodium was observed during this transformation. The rhodium-rhodium interactions were disrupted when an alkene (3-butenol) was added to the aqueous solution. The kinetics of the hydrogenation reaction were measured using a novel high-pressure flow-through NMR system and the catalyst was found to have a TOF of 3000/Rh/h at 25 °C for the hydrogenation of 3-butenol in water.

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