Investigations of LiP(SiMe2CH2SiMe3)–PtBu2, the Surprising Byproduct in the Metalation of (Me3Si)2P–PtBu2

Ewald Sattler, Tibor Szilvási, Eberhard Matern, P. Bombicz, Michael Gamer, Alexander Okrut, Ilona Kovács

Research output: Contribution to journalArticle


During the metalation reaction of (Me3Si)2P–PtBu2 with nBuLi, a byproduct with the sum formula Li(thf)nP(SiMe2CH2SiMe3)–PtBu2 (2, n = 2.7–1) was detected. The formation of the unexpected substituent SiMe2CH2SiMe3 was investigated, a possible reaction mechanism based on DFT calculations established, and the compound synthesized following an independent route. Compound 2 eliminated thf in vacuo to yield the dimeric [Li(thf)P(SiMe2CH2SiMe3)–PtBu2]2 (2a). Exchange of thf with tmeda [Me2N(CH2)2NMe2] in 2 led to the solvent-separated ion pair [Li(tmeda)2]+[(SiMe2CH2SiMe3)P–PtBu2] (4). The solid-state structures of 2a, 4, and the contact ion pair Li(thf)(tmeda)P(SiMe2CH2SiMe3)–PtBu2 (5) were determined by single-crystal X-ray diffraction analysis. Extensive variable-temperature multinuclear NMR studies were carried out to elucidate the structures of these compounds in solution and to compare them with the solid-state structures.

Original languageEnglish
Pages (from-to)5521-5528
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Issue number46
Publication statusPublished - Dec 15 2017



  • Density functional calculations
  • Diphosphanides
  • Donor ligands
  • Lithium
  • NMR spectroscopy
  • Structure elucidation

ASJC Scopus subject areas

  • Inorganic Chemistry

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