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New Acylhydrido- and Diacylrhodium(III) Organocomplexes Derived from 8-Quinolinecarbaldehyde and/or o-(Diphenylphosphanyl)benzaldehyde

  1. Montserrat Barquín1,
  2. María A. Garralda1,
  3. Ricardo Hernández1,
  4. Lourdes Ibarlucea1,
  5. Claudio Mendicute-Fierro1,
  6. M. Carmen Torralba2,
  7. M. Rosario Torres2,
  8. Virginia San Nacianceno1,
  9. Itziar Zumeta1

Article first published online: 14 DEC 2011

DOI: 10.1002/ejic.201100904

Issue

European Journal of Inorganic Chemistry

European Journal of Inorganic Chemistry

Special Issue: Organometallic Chemistry (Cluster Issue)

Volume 2012, Issue 9, pages 1445–1452, March 2012

Additional Information

How to Cite

Barquín, M., Garralda, M. A., Hernández, R., Ibarlucea, L., Mendicute-Fierro, C., Torralba, M. C., Torres, M. R., San Nacianceno, V. and Zumeta, I. (2012), New Acylhydrido- and Diacylrhodium(III) Organocomplexes Derived from 8-Quinolinecarbaldehyde and/or o-(Diphenylphosphanyl)benzaldehyde. Eur. J. Inorg. Chem., 2012: 1445–1452. doi: 10.1002/ejic.201100904

Author Information

  1. 1

    Facultad de Química de San Sebastián, Universidad del País Vasco, Apdo. 1072, 20080 San Sebastián, Spain

  2. 2

    Departamento de Química Inorgánica, Laboratorio de Difracción de Rayos X, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid, Spain

Publication History

  1. Issue published online: 14 MAR 2012
  2. Article first published online: 14 DEC 2011
  3. Manuscript Received: 26 AUG 2011

Funded by

  • Ministerio de Ciencia e Innovación(MICINN). Grant Number: CTQ2008-2967/BQU
  • Universidad del País Vasco
  • Diputación Foral de Gipuzkoa

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Keywords:

  • Rhodium;
  • Chelates;
  • Acyl li­gands;
  • Hydrogenation

Abstract

The acylhydridorhodium(III) complex [RhHCl{PPh2(o-C6H4CO)}(py)2] (1) reacts with 8-quinolinecarbaldehyde (C9H6NCHO) to afford mixed diacyl [RhCl(C9H6NCO){PPh2(o-C6H4CO)}(py)] (2) with acyl groups trans to chlorine and to pyridine. Complex 1 undergoes displacement of pyridine by 2-(aminomethyl)pyridine (ampy) or diphosphanes to give hydridoacyl neutral [RhHCl{PPh2(o-C6H4CO)}(LL)] [LL = ampy (3), bis(diphenylphosphanyl)methane (dppm, 5), 1,3-bis(diphenylphosphanyl)propane (dppp, 6), 1,2-bis(diphenylphosphanyl)ethane (dppe, 7)] with hydride trans to chloride. Complex 3 exchanges hydride with chloride to give [Rh(Cl)2{PPh2(o-C6H4CO)}(ampy)] (4). The reaction of 2 with bidentate N-donor ligands yields cationic mixed diacyl [Rh(C9H6NCO){PPh2(o-C6H4CO)}(NN)]+ species [NN = 2,2′-bipyridine (bipy, 8), ampy (9)]. Neutral or cationic diacyl complexes that contain two acylquinoline fragments can be obtained by the reaction of dimer [Rh(μ-Cl)(C9H6NCO)2]2 (10) with pyridine to give [Rh(Cl)(C9H6NCO)2(py)] (11) or with bidentate N- or P-donor ligands (LL) to afford [Rh(C9H6NCO)2(LL)]+ [LL = dppm (12), dppe (13), dppp (14), 1,4-bis(diphenylphosphanyl)butane (15), ampy (16), 8-aminoquinoline (17), biacetyldihydrazone (18), bipy (19)] with the acyl groups trans to LL. Complex 11 is highly fluxional in solution. At low temperatures, the acylquinoline chelate opens to allow an intramolecular exchange between 11a and 11b (ΔH‡ = 10.1 ± 0.2 kcal mol–1 and ΔS‡ = 1.0 ± 0.1 cal K–1 mol–1), and pyridine dissociation occurs at room temperature. All the complexes were characterized spectroscopically. Single crystal X-ray diffraction analysis was performed on 2.

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