Reversible Insertion of a C═C Bond into Magnesium(I) Dimers: Generation of Highly Active 1,2-Dimagnesioethane Compounds

Aaron J Boutland; Ashlea Carroll; Carlos Alvarez Lamsfus; Andreas Stasch; Laurent Maron; Cameron Jones

doi:10.1021/jacs.7b11368

Reversible Insertion of a C═C Bond into Magnesium(I) Dimers: Generation of Highly Active 1,2-Dimagnesioethane Compounds

J Am Chem Soc. 2017 Dec 20;139(50):18190-18193. doi: 10.1021/jacs.7b11368. Epub 2017 Dec 8.

Authors

Aaron J Boutland¹, Ashlea Carroll¹, Carlos Alvarez Lamsfus², Andreas Stasch¹, Laurent Maron², Cameron Jones¹

Affiliations

¹ School of Chemistry, Monash University , P.O. Box 23, Melbourne, VIC 3800, Australia.
² Université de Toulouse et CNRS , INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, F-31077 Toulouse, France.

PMID: 29206455
DOI: 10.1021/jacs.7b11368

Abstract

The insertion of 1,1-diphenylethylene into the Mg-Mg bond of two magnesium(I) dimers, [(^ArNacnac)Mg-]₂ (Ar = C₆H₂Me₃-2,4,6 (Mes); C₆H₃Et₂-2,6 (Dep)), yielding 1,2-dimagnesioethane products, [{(^ArNacnac)Mg}₂(μ-CH₂CPh₂)], is described. These reactions are readily reversible at room temperature and thus represent the first examples of room-temperature reversible redox processes for s-block metal complexes. The 1,2-dimagnesioethane products are highly activated magnesium alkyls and show unprecedented, uncatalyzed reactivity toward H₂, CO, and ethylene. Computational studies have investigated the mechanisms of all presented reaction types.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't