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

Milko 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

Research output: Contribution to journalArticle

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Abstract

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
Volume357
Issue number6
DOIs
Publication statusPublished - Apr 20 2004

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Ruthenium
Carbon Monoxide
Discrete Fourier transforms
ruthenium
Theoretical Models
Metals
metals
Molecular structure
halides
molecular structure
Diffraction
Single crystals
interactions
vapor phases
X rays
Atoms
Electrons
single crystals
Molecular Structure
Gases

Keywords

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

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

sp3 C-H and sp2 C-H agostic ruthenium complexes : A combined experimental and theoretical study. / van der Boom, Milko; Iron, Mark A.; Atasoylu, Onur; Shimon, Linda J W; Rozenberg, Haim; Ben-David, Yehoshoa; Konstantinovski, Leonid; Martin, Jan M L; Milstein, David.

In: Inorganica Chimica Acta, Vol. 357, No. 6, 20.04.2004, p. 1854-1864.

Research output: Contribution to journalArticle

van der Boom, M, Iron, MA, Atasoylu, O, Shimon, LJW, Rozenberg, H, Ben-David, Y, Konstantinovski, L, Martin, JML & Milstein, D 2004, 'sp3 C-H and sp2 C-H agostic ruthenium complexes: A combined experimental and theoretical study', Inorganica Chimica Acta, vol. 357, no. 6, pp. 1854-1864. https://doi.org/10.1016/j.ica.2003.11.014
van der Boom, Milko ; Iron, Mark A. ; Atasoylu, Onur ; Shimon, Linda J W ; Rozenberg, Haim ; Ben-David, Yehoshoa ; Konstantinovski, Leonid ; Martin, Jan M L ; Milstein, David. / sp3 C-H and sp2 C-H agostic ruthenium complexes : A combined experimental and theoretical study. In: Inorganica Chimica Acta. 2004 ; Vol. 357, No. 6. pp. 1854-1864.
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AU - Iron, Mark A.

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AU - Shimon, Linda J W

AU - Rozenberg, Haim

AU - Ben-David, Yehoshoa

AU - Konstantinovski, Leonid

AU - Martin, Jan M L

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AB - 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.

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