Synthesis and Characterization of a Triphenyl‐Substituted Radical and an Unprecedented Formation of a Carbene‐Functionalized Quinodimethane. Issue 30 (24th March 2014)

• Record Type: Journal Article
• Authors: Mondal, Kartik Chandra; Samuel, Prinson P.; Roesky, Herbert W.; Niepötter, Benedikt; Herbst‐Irmer, Regine; Stalke, Dietmar; Ehret, Fabian; Kaim, Wolfgang; Maity, Bholanath; Koley, Debasis
• Is Part Of: Chemistry. Volume 20:Issue 30(2014)
• Page Start: 9240
• Page End: 9245
• Publication Date: 2014-03-24
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201400393
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The trichlorosilylcarbene monoradical (CycAAC<inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pght94768t" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201400393:tex2gif-sup-1" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>.</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msup></mml:math></alternatives></inline-formula>)SiCl<sub>3</sub> (<bold>1</bold>) was directly converted to (CycAAC<inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pght94766s" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201400393:tex2gif-sup-3" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>.</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msup></mml:math></alternatives></inline-formula>)SiPh<sub>3</sub> (<bold>2</bold>) by substitution of the three chlorine atoms with phenyl groups without affecting the radical center adjacent to the silicon atom. In addition to the structure determination, compound <bold>2</bold> was studied by EPR spectroscopy and DFT calculations. The three hyperfine lines in the EPR spectrum of <bold>2</bold> are due to the coupling with <sup>14</sup>N nucleus. Functionalized 1, 4‐quinodimethane Me<sub>2</sub>cAACC<sub>6</sub>H<sub>4</sub>CPh<sub>2</sub> (<bold>7</bold>) was isolated, whereas carbon analogue of radical <bold>2</bold> was targeted. Cyclic voltammogram of <bold>7</bold> indicated that a stable radical‐anion <bold>7</bold><inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pght9475x5" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201400393:tex2gif-sup-6" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>.</mml:mtext></mml:mrow></mml:msup><mml:mtext mathvariant="bold">−</mml:mtext></mml:mrow></mml:msup></mml:math></alternatives></inline-formula>, as well as a radical‐cation <bold>7</bold><inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pght94760p" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201400393:tex2gif-sup-8" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>.</mml:mtext></mml:mrow></mml:msup><mml:mtext mathvariant="bold">+</mml:mtext></mml:mrow></mml:msup></mml:math></alternatives></inline-formula>, can be prepared. Theoretical calculations showed that one‐electron ionization energy and electron affinity of <bold>7</bold> are 5.1 and 0.7 eV mol<sup>−1</sup>, respectively.</p> </abstract>