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Anionic T-Shaped Platinum(0) Pincer Complexes and Platinum(I) Intermediates in Radical Reactions With Alkyl Halides
Vincenz J Kohler1, Julia Rößling1, Tim M Diederich1
1Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Heidelberg, Germany.
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Two anionic T-shaped d10 platinum(0) complexes supported by a sterically demanding carbazole-based PNP ligand were obtained by reduction of a platinum(II) chloride precursor and characterized as contact ion aggregates 2-Na and 2-Mg with the Na+ and [MgCl(thf)2]+ counterions, respectively. Reactions with organyl bromides produced the homocoupled hydrocarbons and the platinum(II) bromide and alkyl species, depending on the stability of the generated radicals. In situ EPR spectroscopic studies allowed the detection of the transient T-shaped 15-electron platinum(I) metalloradical (giso = 2.219 and a hyperfine coupling (HFC) interaction with a 195Pt atom Aiso of 2124 MHz) involved in the sequential single-electron transfer steps.
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