Mechanistic study of competitive sp3-sp3 and sp 2-sp3 carbon-carbon reductive elimination from a platinum (IV) center and the isolation of a C-C agostic complex

Academic Article

Abstract

  • The addition of methyl triflate to an [NCN]PtCH3 pincer complex 1 ([NCN] = 2,6-bis(diethylaminomethyl)phenyl) results in kinetically controlled competitive reductive eliminations to generate both sp3-sp3 coupling products (ethane and [NCN]Pt(OTf), 3) and an sp2-sp3 coupling product, [[NC(CH3)N]PtCH3][OTf] (4). The last is a cationic complex that could either be formulated as an arenium species or, more likely, as a C-C agostic complex. The addition of CD3OTf to 1 affords 3, CH3CD3, and 4-d3, with the deuterated label in 4-d3 distributed between the arene methyl group and the platinum-bound methyl group, implicating the intermediacy of the five coordinate intermediate [[NCN]Pt(CH3)(CD3)]+ (I-d3). Copyright © 2007 American Chemical Society.
  • Authors

    Digital Object Identifier (doi)

    Author List

  • Madison BL; Thyme SB; Keene S; Williams BS
  • Start Page

  • 9538
  • End Page

  • 9539
  • Volume

  • 129
  • Issue

  • 31