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: mercury -- platinum -- silyl radicals -- trinuclear complexes -- zinc; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201505805
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The thermally stable [( t BuMe2 Si)2 M] (M=Zn, Hg) generate R3 Si . radicals in the presence of [(dmpe)Pt(PEt3 )2 ] at 60–80 °C. The reaction proceeds via hexacoordinate Pt complexes, (M=Zn (2 a and 2 b ), M=Hg (3 a and 3 b )) which were isolated and characterized. Mild warming or photolysis of 2 or 3 lead to homolytic dissociation of the PtMSiR3 bond generating silyl radicals and novel unstable pentacoordinate platinum paramagnetic complexes (M=Zn (5 ), Hg (6 )) whose structures were determined by EPR spectroscopy and DFT calculations. Abstract : SiM City : The thermally stable [( t BuMe2 Si)2 M] (M=Zn, Hg) generate R3 Si . radicals in the presence of [(dmpe)Pt(PEt3 )2 ]. The enhancing effect of the Pt complex on the homolytic cleavage of the SiM bonds in [( t BuMe2 Si)2 M] is mediated by formation of octahedral hexacoordinate PtM trinuclear complexes.