Diastereoselective Template Synthesis on Iron and Uranium [electronic resource]
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| Format: | Government Document Electronic eBook |
| Language: | English |
| Published: |
Washington, D.C. : Oak Ridge, Tenn. :
United States. Department of Energy. Office of Science ; Distributed by the Office of Scientific and Technical Information, U.S. Department of Energy,
2021.
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| Abstract: | The addition of 2 equiv of <em><sup>t</sup></em>Bu<sub>2</sub>PSiMe<sub>3</sub> to 2,6-pyridinedicarboxaldehyde ((CHO)<sub>2</sub>Py) results in a <em>rac</em>/<em>meso</em> diastereomeric mixture of the PNP-chelating ligand 2,6-bis((trimethylsiloxy)(di-<em>tert</em>-butylphosphino)-methyl)-pyridine (<sup>(OTMS)</sup>PNP<sup><em>t</em>Bu</sup>) (<b>1</b>-<em>r</em>/<em>m</em>) via addition of the P?Si bond across both of the aldehyde C?O bonds. Chelation of <sup>(OTMS)</sup>PNP<sup><em>t</em>Bu</sup> to FeCl<sub>2</sub> results in the same diastereotopic ratio of (<sup>(OTMS)</sup>PNP<sup><em>t</em>Bu</sup>)FeCl<sub>2</sub> (<b>2-</b><em>r</em>/<em>m</em>) as the free ligand. Fractional crystallization allows for the isolation of the <em>C</em><sub>2</sub> isomer, <b>2-</b><em>r</em>, and a template synthesis protocol allows for the synthesis and isolation of the <em>C</em><sub>s</sub> isomer, <b>2-</b><em>m</em>, in good yield. Furthermore, the template synthesis protocol was also expanded to the <em>f</em>-block with the use of UCl<sub>4</sub> in order to assess the specificity of the template synthesis on a larger metal cation. This reaction performed on UCl<sub>4</sub> forms the <em>meso</em> diastereospecific uranium complex (<sup>(<em>t</em>Bu2P)</sup>ONO)UCl<sub>2</sub>(dtbpy), <b>3</b>-<em>m</em>, with observation of the rational intermediate (<sup>(OTMS)</sup>PNO<sup><em>t</em>Bu</sup>)UCl<sub>3</sub>(dtbpy), <b>4</b>-<em>m</em>, which arose from the respective formation of two- or one-equivalents of TMS?Cl and formation of the corresponding U?O bond. |
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| Item Description: | Published through Scitech Connect. 07/09/2021. "LA-UR-21-20777." "Journal ID: ISSN 0276-7333." Carpenter, Stephanie H. ; Billow, Brennan S. ; Tondreau, Aaron M. ; |
| Physical Description: | Size: p. 2389-2393 : digital, PDF file. |