Probing the presence of multiple metal-metal bonds in technetium chlorides by X-ray absorption spectroscopy: Implications for synthetic chemistry
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Output type: Journal article
Author list: Poineau F., Johnstone E., Forster P., Ma L., Sattelberger A., Czerwinski K.
Publisher: American Chemical Society
Publication year: 2012
Journal: Inorganic Chemistry (0020-1669)
Volume number: 51
Issue number: 17
Start page: 9563
End page: 9570
Number of pages: 8
ISSN: 0020-1669
eISSN: 1520-510X
URL: http://api.elsevier.com/content/abstract/scopus_id:84865763435
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Abstract
The cesium salts of [TcX] (X = Cl, Br), the reduction product of (n-BuN)[TcOCl] with (n-BuN)BH in THF, and the product obtained from reaction of Tc(OCCH)Cl with HCl(g) at 300 °C have been characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. For the [TcX] anions, the Tc-Tc separations found by EXAFS spectroscopy (2.12(2) Å for both X = Cl and Br) are in excellent agreement with those found by single-crystal X-ray diffraction (SCXRD) measurements (2.117[4] Å for X = Cl and 2.1265(1) Å for X = Br). The Tc-Tc separation found by EXAFS in these anions is slightly shorter than those found in the [TcX ] anions (2.16(2) Å for X = Cl and Br). Spectroscopic and SCXRD characterization of the reduction product of (n-Bu N)[TcOCl] with (n-BuN)BH are consistent with the presence of dinuclear species that are related to the [TcCl] (n = 2, 3) anions. From these results, a new preparation of (n-BuN)[Tc Cl] was developed. Finally, EXAFS characterization of the product obtained from reaction of Tc(OCCH )Cl with HCl(g) at 300 °C indicates the presence of amorphous α-TcCl. The Tc-Tc separation (i.e., 2.46(2) Å) measured in this compound is consistent with the presence of Tc=Tc double bonds in the [Tc] core. © 2012 American Chemical Society.
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