Consecutive cyclometalation by platinum(II)

Milko van der Boom, Shyh Yeon Liou, Linda J W Shimon, Yehoshoa Ben-David, David Milstein

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34 Citations (Scopus)

Abstract

The mechanism of the selective formation of the new benzylic mono- and bicyclometalated platinum(II) complexes 2a,b and 3b has been studied. Monitoring the initial sp3 C-H activation of the ligand DIPPIDH (α2-(diisopropylphosphino)isodurene; 1) and (1,5-cyclooctadiene)dimethylplatinum(II) ((COD)PtMe2) at room temperature by 31P{1H} NMR reveals that, after displacement of 1,5-cyclooctadiene, the complex cis-(DIPPIDH)(DIPPID)-PtMe (2a) is formed selectively by oxidative addition of a benzylic C-H bond and subsequent reductive elimination of CH4. This reaction is controlled by electronic factors. Heating of 2a results in isomerization to the thermodynamically more stable isomer trans-(DIPPIDH)-(DIPPID)PtMe (2b) as well as the formation of the double-C-H activated complex trans-(DIPPID)2Pt (3b) with liberation of CH4 in parallel pathways. Continuous heating results in the quantitative formation of the thermally stable 3b. Mechanistically, the second C-H activation proceeds analogously to the first one. The molecular structure of 3b, possessing two six-membered metallacycles, two methylene bridges, and two phosphines in mutually trans positions, was determined by complete single-crystal diffraction studies.

Original languageEnglish
Pages (from-to)2562-2568
Number of pages7
JournalOrganometallics
Volume15
Issue number10
Publication statusPublished - May 14 1996

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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  • Cite this

    van der Boom, M., Liou, S. Y., Shimon, L. J. W., Ben-David, Y., & Milstein, D. (1996). Consecutive cyclometalation by platinum(II). Organometallics, 15(10), 2562-2568.