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 L)Cr(NO ) (NO). This is shown by a variety of sp...

Full description

Saved in:
Bibliographic Details
Published in:Chemical science (Cambridge) 2019-01, Vol.10 (2), p.475-479
Main Authors: Seo, Junghee, Cabelof, Alyssa C, Chen, Chun-Hsing, Caulton, Kenneth G
Format: Article
Language:English
Subjects:
Chemical reduction
Crystal structure
Crystallography
Deoxygenation
Nitrates
NMR
Nuclear magnetic resonance
Reagents
Trivalent chromium
X ray photoelectron spectroscopy
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 L)Cr(NO ) (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.
ISSN:2041-6520
2041-6539
DOI:10.1039/c8sc02979b