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Ligand-Modification Effects on the Reactivity, Solubility, and Stability of Organometallic Tantalum Complexes in Water

  1. Dr. Ana Conde1,
  2. Dr. Rosa Fandos1,*,
  3. Dr. Carolina Hernández1,
  4. Prof. Dr. Antonio Otero2,*,
  5. Dr. Ana Rodríguez3,
  6. Dr. María José Ruiz1

Article first published online: 20 JAN 2012

DOI: 10.1002/chem.201103026

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 18, Issue 8, pages 2319–2326, February 20, 2012

Additional Information

How to Cite

Conde, A., Fandos, R., Hernández, C., Otero, A., Rodríguez, A. and Ruiz, M. J. (2012), Ligand-Modification Effects on the Reactivity, Solubility, and Stability of Organometallic Tantalum Complexes in Water. Chem. Eur. J., 18: 2319–2326. doi: 10.1002/chem.201103026

Author Information

  1. 1

    Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla-La Mancha, Instituto de Nanociencia, Nanotecnología y Materiales Moleculares (INAMOL), Facultad de Ciencias del Medio Ambiente, Avda. Carlos III, s/n, 45071 Toledo (Spain), Fax: (+34) 925268840

  2. 2

    Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla-La Mancha, Facultad de Químicas, Campus de Ciudad Real, Avd. Camilo José Cela, 10, 13071 Ciudad Real (Spain), Fax: (+34) 926295318

  3. 3

    Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla-La Mancha, ETS Ingenieros Industriales, Campus de Ciudad Real, Avd. Camilo José Cela, 3,13071 Ciudad Real (Spain)

*Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla-La Mancha, Instituto de Nanociencia, Nanotecnología y Materiales Moleculares (INAMOL), Facultad de Ciencias del Medio Ambiente, Avda. Carlos III, s/n, 45071 Toledo (Spain), Fax: (+34) 925268840

Publication History

  1. Issue published online: 10 FEB 2012
  2. Article first published online: 20 JAN 2012
  3. Manuscript Received: 27 SEP 2011

Funded by

  • Ministerio de Ciencia e Innovación. Grant Numbers: CTQ2008-00318/BQU, 2010 ORFEO CSD2007-00006
  • Junta de Comunidades de Castilla-La Mancha. Grant Number: No. PCI08-0010

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Keywords:

  • alkoxides;
  • ligand effects;
  • organometallic complexes;
  • pincer ligands;
  • tantalum

Abstract

Tantalum complexes [TaCp*Me{κ4-C,N,O,O-(OCH2)(OCHC(CH2NMe2)[DOUBLE BOND]CH)py}] (4) and [TaCp*Me{κ4-C,N,O,O-(OCH2)(OCHC(CH2NH2)[DOUBLE BOND]CH)py}] (5), which contain modified alkoxide pincer ligands, were synthesized from the reactions of [TaCp*Me{κ3-N,O,O-(OCH2)(OCH)py}] (Cp*=η5-C5Me5) with HC[TRIPLE BOND]CCH2NMe2 and HC[TRIPLE BOND]CCH2NH2, respectively. The reactions of [TaCp*Me{κ4-C,N,O,O-(OCH2)(OCHC(Ph)[DOUBLE BOND]CH)py}] (2) and [TaCp*Me{κ4-C,N,O,O-(OCH2)(OCHC(SiMe3)[DOUBLE BOND]CH)py}] (3) with triflic acid (1:2 molar ratio) rendered the corresponding bis-triflate derivatives [TaCp*(OTf)2{κ3-N,O,O-(OCH2)(OCHC(Ph)[DOUBLE BOND]CH2)py}] (6) and [TaCp*(OTf)2{κ3-N,O,O-(OCH2)(OCHC(SiMe3)[DOUBLE BOND]CH2)py}] (7), respectively. Complex 4 reacted with triflic acid in a 1:2 molar ratio to selectively yield the water-soluble cationic complex [TaCp*(OTf){κ4-C,N,O,O-(OCH2)(OCHC(CH2NHMe2)[DOUBLE BOND]CH)py}]OTf (8). Compound 8 reacted with water to afford the hydrolyzed complex [TaCp*(OH)(H2O){κ3-N,O,O-(OCH2)(OCHC(CH2NHMe2)[DOUBLE BOND]CH2)py}](OTf)2 (9). Protonation of compound 8 with triflic acid gave the new tantalum compound [TaCp*(OTf){κ4-C,N,O,O-(OCH2)(HOCHC(CH2NHMe2)[DOUBLE BOND]CH)py}](OTf)2 (10), which afforded the corresponding protonolysis derivative [TaCp*(OTf)2{κ3-N,O,O-(OCH2)(HOCHC(CH2NHMe2)[DOUBLE BOND]CH2)py}](OTf) (11) in solution. Complex 8 reacted with CNtBu and potassium 2-isocyanoacetate to give the corresponding iminoacyl derivatives 12 and 13, respectively. The molecular structures of complexes 5, 7, and 10 were established by single-crystal X-ray diffraction studies.

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