Activation of Homolytic Si-Zn and Si-Hg Bond Cleavage, Mediated by a Pt(0) Complex, via Novel Pt-Zn and Pt-Hg Compounds.
The thermally stable [(tBuMe2 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.
Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel).
Yosi
Y
Kratish
Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel).
Gregory
G
Molev
Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel).
Arseni
A
Kostenko
Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel).
Dennis
D
Sheberla
Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel).
Boris
B
Tumanskii
Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel).
Mark
M
Botoshansky
Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565 (Japan).
Shigeru
S
Shimada
Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel). chrbrzh@tx.technion.ac.il.
Dmitry
D
Bravo-Zhivotovskii
Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel). apeloig@technion.ac.il.
Yitzhak
Y
Apeloig
mercury; platinum; silyl radicals; trinuclear complexes; zinc