Zwitterionic weak-link approach complexes based on anionic icosahedral monocarbaboranes

Robert D. Kennedy, Charlotte L. Stern, Chad A. Mirkin*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

14 Scopus citations


The anionic hemilabile phosphinothioether ligand, [1-(Ph 2PCH2CH2S)-closo-1-CB11H 11 ]-, which is functionalized with an anionic icosahedral monocarbaborane anion, was synthesized in three steps from [HNMe 3][closo-CB11H12]. The ligand was used to synthesize a family of zwitterionic Weak-Link Approach (WLA) complexes that contain platinum(II), palladium(II), and rhodium(I). These complexes were characterized using multinuclear NMR spectroscopy, high-resolution mass spectrometry, and single-crystal X-ray diffraction analyses. Although the C-bound [closo-CB11H11]- anion behaves as an electron-withdrawing moiety, hemilabile phosphinothioether ligands that are based on this unit are strongly chelating, as determined via the measurement of the chloride association constant. The chelating strength is comparable to that of hemilabile ligands that are functionalized with the very electron-rich B-bound closo-1,7-C2B10H11 moiety, thus demonstrating the use of charge to influence ligand coordination strength. The anionic Rh(I) WLA complex that is synthesized using this ligand can act as the noncoordinating anion of a regular cationic Rh(I) WLA complex. Thus, an unprecedented type of salt, in which the anion and cation are mutually isostructural and isoelectronic WLA complexes, has been synthesized and characterized crystallographically.

Original languageEnglish (US)
Pages (from-to)14064-14071
Number of pages8
JournalInorganic chemistry
Issue number24
StatePublished - Dec 16 2013

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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