Reactivity of HTcO4 with methanol in sulfuric acid: Tc-sulfate complexes revealed by XAFS spectroscopy and first principles calculations

Frederic Poineau; Philippe F. Weck; Benjamin P. Burton-Pye; Ibthihel Denden; Eunja Kim; William Kerlin; Konstantin E. German; Massoud Fattahi; Lynn C. Francesconi; Alfred P. Sattelberger; Kenneth R. Czerwinski

doi:10.1039/C3DT32951H

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Dalton Transactions

Issue 13, 2013

The international journal for inorganic, organometallic and bioinorganic chemistry

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Reactivity of HTcO₄ with methanol in sulfuric acid: Tc-sulfate complexes revealed by XAFS spectroscopy and first principles calculations

Frederic Poineau,*^a Philippe F. Weck,^b Benjamin P. Burton-Pye,^c Ibthihel Denden,^d Eunja Kim,^e William Kerlin,^a Konstantin E. German,^f Massoud Fattahi,^d Lynn C. Francesconi,^c Alfred P. Sattelberger^g and Kenneth R. Czerwinski^a

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Department of Chemistry, University of Nevada Las Vegas, Las Vegas, USA
E-mail: poineauf@unlv.nevada.edu

Sandia National Laboratories, Albuquerque, USA

Department of Chemistry, Hunter College of the City University of New York, USA

Laboratory Subatech, Ecoles des Mines de Nantes, Nantes, France

Department of Physics and Astronomy, University of Nevada Las Vegas, Las Vegas, USA

A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 119071 Moscow, Russian Federation

Energy Engineering and Systems Analysis Directorate, Argonne National Laboratory, Lemont, USA

Dalton Trans., 2013,42, 4348-4352

DOI: 10.1039/C3DT32951H
Received 11 Sep 2012, Accepted 20 Jan 2013
First published online 23 Jan 2013

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The reaction between HTcO₄ and MeOH in 13 M H₂SO₄ was investigated by ⁹⁹Tc NMR, UV-visible and X-ray absorption fine structure (XAFS) spectroscopy. Experimental results and first principles calculations show the formation of Tc(+5) sulfate complexes. The results expand the fundamental understanding of Tc in high acid solutions.

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Reactivity of HTcO₄ with methanol in sulfuric acid: Tc-sulfate complexes revealed by XAFS spectroscopy and first principles calculations

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Reactivity of HTcO4 with methanol in sulfuric acid: Tc-sulfate complexes revealed by XAFS spectroscopy and first principles calculations

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Reactivity of HTcO₄ with methanol in sulfuric acid: Tc-sulfate complexes revealed by XAFS spectroscopy and first principles calculations