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

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Abstract

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
Volume61
Issue number19
Early online date25 Feb 2022
DOIs
Publication statusPublished - 2 May 2022

Keywords

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

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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