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Title: Photochemical behavior of the quadruply metal-metal bonded [Tc 2Cl 8] 2– anion in acetonitrile

Abstract

Here, the photochemical behavior of [Tc 2Cl 8] 2– was investigated in acetonitrile. The speciation of Tc before and after irradiation at 254 nm was performed by UV-visible spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Upon irradiation at 254 nm, [Tc 2Cl 8] 2– was unstable, the scission of the Tc ≡ Tc unit occurred and the complex [TcCl 4(CH 3CN) 2] was identified. The disappearance rate of [M 2Cl 8] 2– (M = Tc, Re) under irradiation has been measured and was ~7.5 time faster for Tc than for Re.

Authors:
 [1];  [2];  [2];  [2];  [3];  [4]
  1. Hunter College of the City Univ. of New York, New York City, NY (United States); Lehman College of the City Univ. of New York, New York City, NY (United States); The Graduate Center of the City Univ. of New York, New York, NY (United States)
  2. Univ. of Nevada, Las Vegas, NV (United States)
  3. Hunter College of the City Univ. of New York, New York City, NY (United States); The Graduate Center of the City Univ. of New York, New York, NY (United States)
  4. Univ. of Nevada, Las Vegas, NV (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
University of Nevada–Las Vegas; National Institutes of Health (NIH); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1339611
Grant/Contract Number:
AC02-06CH11357; FG02-09ER16097; SC0002456
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganica Chimica Acta
Additional Journal Information:
Journal Volume: 453; Journal Issue: C; Journal ID: ISSN 0020-1693
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; technetium; metal-metal multiple bonds; photochemistry

Citation Formats

Burton-Pye, Benjamin P., Poineau, Frederic, Bertoia, Julie, Czerwinski, Kenneth R., Francesconi, Lynn C., and Sattelberger, Alfred P. Photochemical behavior of the quadruply metal-metal bonded [Tc2Cl8]2– anion in acetonitrile. United States: N. p., 2016. Web. doi:10.1016/j.ica.2016.09.041.
Burton-Pye, Benjamin P., Poineau, Frederic, Bertoia, Julie, Czerwinski, Kenneth R., Francesconi, Lynn C., & Sattelberger, Alfred P. Photochemical behavior of the quadruply metal-metal bonded [Tc2Cl8]2– anion in acetonitrile. United States. doi:10.1016/j.ica.2016.09.041.
Burton-Pye, Benjamin P., Poineau, Frederic, Bertoia, Julie, Czerwinski, Kenneth R., Francesconi, Lynn C., and Sattelberger, Alfred P. 2016. "Photochemical behavior of the quadruply metal-metal bonded [Tc2Cl8]2– anion in acetonitrile". United States. doi:10.1016/j.ica.2016.09.041. https://www.osti.gov/servlets/purl/1339611.
@article{osti_1339611,
title = {Photochemical behavior of the quadruply metal-metal bonded [Tc2Cl8]2– anion in acetonitrile},
author = {Burton-Pye, Benjamin P. and Poineau, Frederic and Bertoia, Julie and Czerwinski, Kenneth R. and Francesconi, Lynn C. and Sattelberger, Alfred P.},
abstractNote = {Here, the photochemical behavior of [Tc2Cl8]2– was investigated in acetonitrile. The speciation of Tc before and after irradiation at 254 nm was performed by UV-visible spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Upon irradiation at 254 nm, [Tc2Cl8]2– was unstable, the scission of the Tc ≡ Tc unit occurred and the complex [TcCl4(CH3CN)2] was identified. The disappearance rate of [M2Cl8]2– (M = Tc, Re) under irradiation has been measured and was ~7.5 time faster for Tc than for Re.},
doi = {10.1016/j.ica.2016.09.041},
journal = {Inorganica Chimica Acta},
number = C,
volume = 453,
place = {United States},
year = 2016,
month = 9
}

Journal Article:
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  • The electronic absorption spectra of Re/sub 2/(piv)/sub 4/Cl/sub 2/ and Re/sub 2/(piv)/sub 4/Br/sub 2/ (piv = O/sub 2/CCMe/sub 3/) have been measured as a function of pressure in the crystalline solids and for the molecules dissolved in PMMA (poly(methyl methacrylate)). High pressure infrared absorption spectra have been measured for the crystalline solids dispersed in mineral oil over the range 700-1800 cm/sup -1/. The major feature appearing in the electronic spectra is the growth in intensity of a band lying on the low-energy side of the delta ..-->.. delta* excitation. This growth starts at the lowest pressures, while only above /approximately/more » 40 kbar is any decrease in intensity of the delta ..-->.. delta* excitation observed. In the region above 25-30 kbar new peaks appear in the ir spectrum at 1134, 1280, and 1697 cm/sup -1/ for the bromide and at 1142, 1286, and 1697 cm/sup -1/ for the chloride. After consideration of alternative possibilities, the changes in the spectra are assigned to a molecular isomerization, in which the axial halide ligands move to radial positions and force two of the bidentate pivalate ligands to become monodentate. 25 references, 9 figures, 1 table.« less
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