Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh3)2(ZnMe)4H2]

Lia Sotorríos, Fedor M. Miloserdov, Anne-Frédérique Pécharman, John P. Lowe, Stuart A Macgregor, Mary F. Mahon, Michael Whittlesey

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)
33 Downloads (Pure)


The syntheses, reactivity and electronic structure analyses of [Ru(PPh3)2(ZnMe)4H2], 1 a, and [Ru(PPh3)2(ZnPh)4H2], 2 b, are reported. 1 a exhibits an 8‐coordinate Ru centre with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe ligands in 1 a undergo facile, sequential exchange with ZnPh2 to give 2 b, which shows a 3 : 1 arrangement of ZnPh ligands. Both 1 a and 2 b exist in equilibrium with their respective 3 : 1 and 2 : 2 isomers. Mechanisms for ZnMe/ZnPh exchange and isomerisation are proposed using DFT calculations. The relationships of these {Ru(ZnR)4H2} species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed.
Original languageEnglish
Article numbere202117495
JournalAngewandte Chemie International Edition
Issue number19
Early online date25 Feb 2022
Publication statusPublished - 2 May 2022


  • Density Functional Calculations
  • Heterometallic Complexes
  • Hydrides
  • Ruthenium
  • Zinc

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry


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