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: | 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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