Activation of Homolytic SiZn and SiHg Bond Cleavage, Mediated by a Pt0 Complex, via Novel PtZn and PtHg Compounds. Issue 40 (18th August 2015)

• Record Type: Journal Article
• Authors: Kratish, Yosi; Molev, Gregory; Kostenko, Arseni; Sheberla, Dennis; Tumanskii, Boris; Botoshansky, Mark; Shimada, Shigeru; Bravo‐Zhivotovskii, Dmitry; Apeloig, Yitzhak
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 40(2015)
• Page Start: 11817
• Page End: 11821
• Publication Date: 2015-08-18
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201505805
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The thermally stable [(<italic>t</italic>BuMe₂Si)₂M] (M=Zn, Hg) generate R₃Si^. radicals in the presence of [(dmpe)Pt(PEt₃)₂] at 60–80 °C. The reaction proceeds via hexacoordinate Pt complexes, (M=Zn (<bold>2 a</bold> and <bold>2 b</bold>), M=Hg (<bold>3 a</bold> and <bold>3 b</bold>)) which were isolated and characterized. Mild warming or photolysis of <bold>2</bold> or <bold>3</bold> lead to homolytic dissociation of the PtMSiR₃ bond generating silyl radicals and novel unstable pentacoordinate platinum paramagnetic complexes (M=Zn (<bold>5</bold>), Hg (<bold>6</bold>)) whose structures were determined by EPR spectroscopy and DFT calculations.</p> </abstract>