Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes
Abstract
Here, a series of metallocene thorium complexes with mono- and bis(phosphido) ligands have been investigated with varying hues: (C5Me5)2Th(Cl)[P(Mes)2] (Mes = mesityl = 2,4,6-(CH3)3C6H2; dark red-purple), (C5Me5)2Th[P(Mes)(CH3)]2 (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)2] (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th(Cl)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th[P(Mes)(SiMe3)]2 (orange), and (C5Me5)2Th[PH(Mes)]2 (pale yellow). While all of these complexes bear a mesityl group on phosphorus, the electronic structure observed differs depending on the other substituent (mesityl, methyl, trimethylsilyl, or hydrogen). This sparked an investigation of the electronic structure of these complexes using 31P NMR and electronic absorption spectroscopy in concert with time-dependent density functional theory calculations.
- Authors:
-
[3];
[4];
[4];
[1]
- Univ. of Missouri, Columbia, MO (United States). Dept. of Chemistry
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. at Buffalo, NY (United States). Dept. of Chemistry
- Univ. at Buffalo, NY (United States). Dept. of Chemistry
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1483515
- Report Number(s):
- LA-UR-18-22942
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 57; Journal Issue: 12; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Rungthanaphatsophon, Pokpong, Duignan, Thomas J., Myers, Alexander J., Vilanova, Sean P., Barnes, Charles L., Autschbach, Jochen, Batista, Enrique R., Yang, Ping, and Walensky, Justin R. Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes. United States: N. p., 2018.
Web. doi:10.1021/acs.inorgchem.8b00922.
Rungthanaphatsophon, Pokpong, Duignan, Thomas J., Myers, Alexander J., Vilanova, Sean P., Barnes, Charles L., Autschbach, Jochen, Batista, Enrique R., Yang, Ping, & Walensky, Justin R. Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes. United States. https://doi.org/10.1021/acs.inorgchem.8b00922
Rungthanaphatsophon, Pokpong, Duignan, Thomas J., Myers, Alexander J., Vilanova, Sean P., Barnes, Charles L., Autschbach, Jochen, Batista, Enrique R., Yang, Ping, and Walensky, Justin R. Fri .
"Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes". United States. https://doi.org/10.1021/acs.inorgchem.8b00922. https://www.osti.gov/servlets/purl/1483515.
@article{osti_1483515,
title = {Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes},
author = {Rungthanaphatsophon, Pokpong and Duignan, Thomas J. and Myers, Alexander J. and Vilanova, Sean P. and Barnes, Charles L. and Autschbach, Jochen and Batista, Enrique R. and Yang, Ping and Walensky, Justin R.},
abstractNote = {Here, a series of metallocene thorium complexes with mono- and bis(phosphido) ligands have been investigated with varying hues: (C5Me5)2Th(Cl)[P(Mes)2] (Mes = mesityl = 2,4,6-(CH3)3C6H2; dark red-purple), (C5Me5)2Th[P(Mes)(CH3)]2 (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)2] (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th(Cl)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th[P(Mes)(SiMe3)]2 (orange), and (C5Me5)2Th[PH(Mes)]2 (pale yellow). While all of these complexes bear a mesityl group on phosphorus, the electronic structure observed differs depending on the other substituent (mesityl, methyl, trimethylsilyl, or hydrogen). This sparked an investigation of the electronic structure of these complexes using 31P NMR and electronic absorption spectroscopy in concert with time-dependent density functional theory calculations.},
doi = {10.1021/acs.inorgchem.8b00922},
journal = {Inorganic Chemistry},
number = 12,
volume = 57,
place = {United States},
year = {Fri Jun 01 00:00:00 EDT 2018},
month = {Fri Jun 01 00:00:00 EDT 2018}
}
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Figure 1: Thermal ellipsoid plots of 1 (left) and 4 (right) shown at the 50% probability level. The hydrogen atoms have been omitted for clarity.
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Works referencing / citing this record:
Thorium(IV) and Uranium(IV) Phosphaazaallenes
journal, August 2019
- Rungthanaphatsophon, Pokpong; Fajen, O. Jonathan; Kelley, Steven P.
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