Kowalski, Konrad and Winter, Rainer F. and Makal, Anna and Pazio, Aleksandra and Wozniak, Krzysztof (2009) The Synthesis, Structure, and FTIR Spectroelectrochemistry of W(CO)(5) Complexes of 4-Oxo-4-(2,5-dimethylazaferrocen-1 '-yl)butanoic and 5-Oxo-5-(2,5-dimethylazaferrocen-1 '-yl)pentanoic Acids. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY (27). pp. 4069-4077. ISSN 1434-1948, 1099-0682
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With the aim of developing new IR-detectable metal-carbonyl tracers for the amino function, we have synthesized W(CO)(5) complexes of 4-oxo-4-(2,5-dimethylazaferrocen-1'-yl)butanoic acid (2) and 5-oxo-5-(2,5-dimethylazaferrocen-1'-yl)pentanoic acid (3) by AlCl3-catalyzed Friedel-Crafts reaction Of W(CO)(5)-2,5-dimethylazaferrocene (1) with succinic or glutaric anhydride. Complexes 2 and 3 are thermally stable and display sharp, intense absorption bands of lungsten-coordinated CO ligands at ca. 1923 cm(-1). In the crystalline state, molecules of 2 and 3 are stabilized by a network of intra- and intermolecular hydrogen bonds, as shown by single-crystal X-ray structure analysis. Complex 2 was transformed into the corresponding N-succinimidyl ester 4. Its utility toward labeling of amino acids was tested in its reaction with glycine methyl ester. Corresponding glycine amide 5 was obtained in 82% yield and is an air/thermally stable bioconjugate exhibiting intense sharp absorption bands of the W-CO reporting group at ca. 1923 cm(-1). Cyclic voltammetry of 1, 2, 3, and acetyl derivative 6 shows the presence of two redox events in each case. The first redox couple is ascribed as an azaferrocene-centered oxidation-reduction, whereas the second, irreversible process at higher potential originates from a W(CO)(5)-centered oxidation. FTIR spectro-electrochemistry allowed us to monitor the spectroscopic changes accompanying the 1/1(.+), 2/2(.+), and 6/6(.+) redox transformations. Significant W-CO absorption band shifts were recorded in the course of these experiments. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ESTROGEN-RECEPTOR MODULATORS; APOPTOSIS-INDUCING ACTIVITY; ELECTRON-TRANSFER; DIASTEREOSELECTIVE FORMATION; NUCLEOSIDE ANALOGS; MIXED-VALENT; ACTIVE-SITE; FERROCENE; FERROCIFEN; CHEMISTRY; Metallocenes; Cyclic voltammetry; IR spectroscopy; X-ray diffraction |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Alumni or Retired Professors > Arbeitskreis Prof. Dr. Rainer Winter Chemistry and Pharmacy > Institut für Anorganische Chemie > Alumni or Retired Professors |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 08 Sep 2020 05:19 |
| Last Modified: | 08 Sep 2020 05:19 |
| URI: | https://pred.uni-regensburg.de/id/eprint/28449 |
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