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

ABSTRACT: 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 (H₂L)Cr(NO₃)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.

SUBMITTER: Seo J

PROVIDER: S-EPMC6335631 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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

Seo Junghee J Cabelof Alyssa C AC Chen Chun-Hsing CH Caulton Kenneth G KG

Chemical science 20181016 2

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 (H2L)Cr(NO3)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 proce ...[more]

PMID: 30746094

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