Selective deoxygenation of nitrate to nitrosyl using trivalent chromium and the Mashima reagent: reductive silylation

1,4-Bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene is an effective silyl transfer reagent towards the oxygen of nitrate coordinated to Cr(iii) in a pincer complex. Two nitrate oxygens are removed to give the 17 valence electron octahedral complex (H(2)L)Cr(NO(3))(2)(NO). This is shown by a variety...

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Detalles Bibliográficos
Autores principales: Seo, Junghee, Cabelof, Alyssa C., Chen, Chun-Hsing, Caulton, Kenneth G.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6335631/
https://www.ncbi.nlm.nih.gov/pubmed/30746094
http://dx.doi.org/10.1039/c8sc02979b
Descripción
Sumario:1,4-Bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene is an effective silyl transfer reagent towards the oxygen of nitrate coordinated to Cr(iii) in a pincer complex. Two nitrate oxygens are removed to give the 17 valence electron octahedral complex (H(2)L)Cr(NO(3))(2)(NO). This is shown by a variety of spectroscopic methods, together with DFT, to be a Cr(i) complex with a linear CrNO unit. This work also identifies future applications of this reductive silylation process.

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