[{SiNDipp}MgNa]2: A potent molecular reducing agent

Liu, Han-Ying, Neale, Samuel E., Hill, Michael S., Mahon, Mary F., McMullin, Claire L. and Richards, Emma ORCID: https://orcid.org/0000-0001-6691-2377 2024. [{SiNDipp}MgNa]2: A potent molecular reducing agent. Organometallics 43 (8) , pp. 879-888. 10.1021/acs.organomet.4c00076

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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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	0276-7333
Funders:	EPSRC
Date of First Compliant Deposit:	10 April 2024
Date of Acceptance:	25 March 2024
Last Modified:	04 Jun 2024 13:07
URI:	https://orca.cardiff.ac.uk/id/eprint/167870

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