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- Title
Zinc‐Promoted ZnMe/ZnPh Exchange in Eight‐Coordinate [Ru(PPh<sub>3</sub>)<sub>2</sub>(ZnMe)<sub>4</sub>H<sub>2</sub>].
- Authors
Sotorrios, Lia; Miloserdov, Fedor M.; Pécharman, Anne‐Frédérique; Lowe, John P.; Macgregor, Stuart A.; Mahon, Mary F.; Whittlesey, Michael K.
- Abstract
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.
- Subjects
TRANSITION metals; EQUILIBRIUM reactions; ELECTRONIC structure; ISOMERIZATION; ISOMERS
- Publication
Angewandte Chemie, 2022, Vol 134, Issue 19, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202117495