[{SiNDipp}MgNa]2: A Potent Molecular Reducing Agent.
Organometallics
; 43(8): 879-888, 2024 Apr 22.
Article
en En
| MEDLINE
| ID: mdl-38665773
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+ â 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.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Organometallics
Año:
2024
Tipo del documento:
Article
País de afiliación:
Reino Unido