Activation of H-2 over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)(2)(CO)ZnEt](+)

Ian M. Riddlestone, Nasir Ahmad Rajabi, John P. Lowe, Mary F. Mahon, Stuart Alan Macgregor, Michael K. Whittlesey

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Abstract

Reaction of [Ru(IPr)(2)(CO)H]BAr4F with ZnEt2 forms the heterobimetallic species [Ru(IPr)(2)(CO)-ZnEt]BAr4F (2), which features an unsupported Ru-Zn bond. 2 reacts with H-2 to give [Ru(IPr)(2)(CO)(eta(2)-H-2)-(H)(2)ZnEt]BAr4F (3) and [Ru(IPr)(2)(CO)(H)(2)ZnEt]BArP4 (4). DFT calculations indicate that H-2 activation at 2 proceeds via oxidative cleavage at Ru with concomitant hydride transfer to Zn. 2 can also activate hydridic E-H bonds (E = B, Si), and computed mechanisms for the facile H/H exchange processes observed in 3 and 4 are presented.

Original languageEnglish
Pages (from-to)11081-11084
Number of pages4
JournalJournal of the American Chemical Society
Volume138
Issue number35
Early online date4 Aug 2016
DOIs
Publication statusPublished - 7 Sep 2016

Keywords

  • NICKEL-BORANE COMPLEX
  • CATALYTIC-HYDROGENATION
  • POLYHYDRIDE COMPLEXES
  • PLATINUM COMPLEXES
  • LIGAND COOPERATION
  • HYDRIDE COMPLEXES
  • ZINC
  • CLEAVAGE
  • COORDINATION
  • DIHYDROGEN

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