sp3 C-H and sp2 C-H agostic ruthenium complexes: A combined experimental and theoretical study

Milko E. Van Der Boom, Mark A. Iron, Onur Atasoylu, Linda J.W. Shimon, Haim Rozenberg, Yehoshoa Ben-David, Leonid Konstantinovski, Jan M.L. Martin, David Milstein

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Halide abstraction from the 18 electron Ru(II) complex RuCl(CO) 2[2,6-(CH2PtBu2)2C 6H3] (2) with AgPF6 results in the exclusive formation of the cationic complex {Ru(CO)2[2,6-(CH2P tBu2)2C6H3]} +PF6- (3). The molecular structures of 2 and 3 were determined by complete single-crystal diffraction studies. X-ray crystallographic analysis of 3 reveals that the "open" coordination site is occupied by an agostic interaction between the metal center and an sp3 C-H bond of a tert-butyl substituent. DFT gas phase calculations (B97-1/SDD) show the necessity of two sterically demanding tert-butyl substituents on one P donor atom for the agostic interaction to occur. The reaction of 3 with H2 results in the quantitative conversion to {Ru(H)(CO)2[2,6-(CH2PtBu2) 2C6H4]}+PF6- (4) where the aromatic Cipso-H bond is η2-coordinated to the metal center. Treatment of the agostic complex 4 with Et3N results in the formation of the neutral complex Ru(H)(CO)2[2,6- (CH2PtBu2)2C6H 3] (5). The mechanistic details of 3+H2→4 were investigated by DFT calculations at the B97-1/SDB-cc-pVDZ//B97-1/SDD level of theory.

Original languageEnglish
Pages (from-to)1854-1864
Number of pages11
JournalInorganica Chimica Acta
Issue number6
Publication statusPublished - Apr 20 2004



  • Agostic interactions
  • Crystal structures
  • DFT
  • Dihydrogen addition
  • Pincer complexes
  • Ruthenium

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Van Der Boom, M. E., Iron, M. A., Atasoylu, O., Shimon, L. J. W., Rozenberg, H., Ben-David, Y., Konstantinovski, L., Martin, J. M. L., & Milstein, D. (2004). sp3 C-H and sp2 C-H agostic ruthenium complexes: A combined experimental and theoretical study. Inorganica Chimica Acta, 357(6), 1854-1864. https://doi.org/10.1016/j.ica.2003.11.014