Technetium cyanide chemistry: synthesis and characterization of technetium(III) and -(V) cyanide complexes
- Massachusetts Inst. of Technology, Cambridge
Several new technetium cyanide complexes have been prepared and characterized. The reaction of ammonium hexaiodotechnetate(IV) with potassium cyanide in refluxing aqueous methanol under nitrogen yields potassium heptacyanotechnetate(III) dihydrate, K/sub 4/Tc(CN)/sub 7/.2H/sub 2/O (1). Infrared and Raman measurements indicate that 1 has a pentagonal bipyramidal structure (D/sub 5h/) in both solid and solution. Aqueous solutions of 1 are air sensitive, decomposing to potassium oxopentacyanotechnetate(V) tetrahydrate, K/sub 2/TcO(CN)/sub 5/.4H/sub 2/O (2). This species can also be prepared from the reaction of TcO/sub 2/.xH/sub 2/O with hot aqueous potassium cyanide solutions. Hydrolysis of 2 in water yields potassium trans-dioxo-tetracyanotechnetate(V), K/sub 3/TcO/sub 2/(CN)/sub 4/ (3). Preparation of 3 can also be achieved from the treatment of (TcO/sub 2/(Py)/sub 4/)ClO/sub 4/.2H/sub 2/O with aqueous potassium cyanide. Infrared and Raman measurements on 3 are consistent with the proposed trans-dioxo (D/sub 4h/) structure. Reaction of the oxotetrachlorotechnetate(V) anion, TcOCl/sub 4/, with potassium cyanide in methanol produces trans-oxomethoxytetracyanotechnetate(V). (TcO(OMe)(CN)/sub 4/) (4). The full details of the synthesis and characterization of these interesting technetium(III) and -(V) complexes, as well as observations on the infrared and Raman spectra of trans-dioxo metal complexes and the hydrolysis of species 2, are presented.
- DOE Contract Number:
- E(11-1)4115
- OSTI ID:
- 5067804
- Journal Information:
- Inorg. Chem.; (United States), Vol. 19:7
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
TECHNETIUM COMPLEXES
CHEMICAL PREPARATION
CHEMICAL PROPERTIES
STRUCTURAL CHEMICAL ANALYSIS
CYANIDES
HYDROLYSIS
INFRARED SPECTRA
POTASSIUM COMPOUNDS
RAMAN SPECTRA
ALKALI METAL COMPOUNDS
CHEMICAL REACTIONS
COMPLEXES
DECOMPOSITION
LYSIS
SOLVOLYSIS
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials