TY - JOUR
T1 - Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh3)2(ZnMe)4H2]
AU - Sotorríos, Lia
AU - Miloserdov, Fedor M.
AU - Pécharman, Anne-Frédérique
AU - Lowe, John P.
AU - Macgregor, Stuart A
AU - Mahon, Mary F.
AU - Whittlesey, Michael
N1 - Funding Information:
We thank the EU's Horizon 2020 research and innovation programme under Marie Skłodowska‐Curie grant agreement No 792674 (to FM) and EPSRC (grants EP/T019876/1 and EP/T019743/1) for funding.
Publisher Copyright:
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
PY - 2022/5/2
Y1 - 2022/5/2
N2 - 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.
AB - 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.
KW - Density Functional Calculations
KW - Heterometallic Complexes
KW - Hydrides
KW - Ruthenium
KW - Zinc
UR - http://www.scopus.com/inward/record.url?scp=85126213701&partnerID=8YFLogxK
U2 - 10.1002/anie.202117495
DO - 10.1002/anie.202117495
M3 - Article
C2 - 35213937
SN - 1433-7851
VL - 61
JO - Angewandte Chemie International Edition
JF - Angewandte Chemie International Edition
IS - 19
M1 - e202117495
ER -