Probing the presence of multiple metal-metal bonds in technetium chlorides by X-ray absorption spectroscopy: implications for synthetic chemistry.
Inorg Chem
; 51(17): 9563-70, 2012 Sep 03.
Article
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| MEDLINE
| ID: mdl-22906536
ABSTRACT
The cesium salts of [Tc(2)X(8)](3-) (X = Cl, Br), the reduction product of (n-Bu(4)N)[TcOCl(4)] with (n-Bu(4)N)BH(4) in THF, and the product obtained from reaction of Tc(2)(O(2)CCH(3))(4)Cl(2) with HCl(g) at 300 °C have been characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. For the [Tc(2)X(8)](3-) 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 [Tc(2)X(8)](2-) anions (2.16(2) Å for X = Cl and Br). Spectroscopic and SCXRD characterization of the reduction product of (n-Bu(4)N)[TcOCl(4)] with (n-Bu(4)N)BH(4) are consistent with the presence of dinuclear species that are related to the [Tc(2)Cl(8)](n-) (n = 2, 3) anions. From these results, a new preparation of (n-Bu(4)N)(2)[Tc(2)Cl(8)] was developed. Finally, EXAFS characterization of the product obtained from reaction of Tc(2)(O(2)CCH(3))(4)Cl(2) with HCl(g) at 300 °C indicates the presence of amorphous α-TcCl(3). The Tc-Tc separation (i.e., 2.46(2) Å) measured in this compound is consistent with the presence of TcâTc double bonds in the [Tc(3)](9+) core.
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MEDLINE
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Revista:
Inorg Chem
Año:
2012
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Article
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Estados Unidos