Abstract
The bimetallic species, [{SiNDipp}MgNa]2 [{SiNDipp} = {CH2SiMe2N(Dipp)}2; (Dipp = 2,6-i-Pr2C6H3)], is shown to be a potent reducing agent, able to effect one- or two-electron reduction of either dioxygen, TEMPO, anthracene, benzophenone, or diphenylacetylene. In most cases, the bimetallic reaction products imply that the dissimilar alkaline metal centers react with a level of cooperativity. EPR analysis of the benzophenone-derived reaction and the concurrent isolation of [{SiNDipp}Mg(OCPh2)2], however, illustrate that treatment with such reducible, but O-basic, species can also result in reactivity in which the metals provide independent reaction products. The notable E-stereochemistry of the diphenylacetylene reduction product prompted a computational investigation of the PhC≡CPh addition. This analysis invokes a series of elementary steps that necessitate ring-opening via Mg+ → Na+ amido group migration of the SiNDipp ligand, providing insight into the previously observed lability of the bidentate dianion and its consequent proclivity toward macrocyclization.
Original language | English |
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Pages (from-to) | 879-888 |
Number of pages | 10 |
Journal | Organometallics |
Volume | 43 |
Issue number | 8 |
Early online date | 9 Apr 2024 |
DOIs | |
Publication status | Published - 22 Apr 2024 |
Funding
The authors gratefully acknowledge EPSRC (EP/X01181 X/1, \u201CMolecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements\u201D) for support of this research. This research made use of the Anatra High Performance Computing (HPC) Service at the University of Bath. The authors gratefully acknowledge the University of Bath\u2019s Research Computing Group (doi.org/10.15125/b6cd-s854) for their support in this work.
Funders | Funder number |
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Engineering and Physical Sciences Research Council | EP/X01181 X/1 |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry