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

Lia Sotorrios, Fedor Miloserdov, Anne-Frédérique Pecharman, John Lowe, Stuart Macgregor, Mary Mahon, Michael Whittlesey

Research output: Contribution to journalArticlepeer-review

3 Citations (SciVal)


The syntheses, reactivity and electronic structure analyses of [Ru(PPh 3 ) 2 (ZnMe) 4 H 2 ], 1a , and [Ru(PPh 3 ) 2 (ZnPh) 4 H 2 ], 2b , are reported. 1a 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 1a undergo facile, sequential exchange with ZnPh 2 to give 2b , which shows a 3:1 arrangement of ZnPh ligands. Both 1a and 2b 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) 4 H 2 } 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 date14 Mar 2022
Publication statusPublished - 2 May 2022


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

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)


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