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Updated: Oct 2, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh3 )2 (ZnMe)4 H2 ]
Lia Sotorrios1, Fedor M Miloserdov2,3, Anne-Frédérique Pécharman2
1Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK.
Abstract:
The syntheses, reactivity and electronic structure analyses of [Ru(PPh3 )2 (ZnMe)4 H2 ], 1 a, and [Ru(PPh3 )2 (ZnPh)4 H2 ], 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)4 H2 } species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed.
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