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Redox-Controlled and Reversible N–N Bond Forming and Splitting with an IronIVTerminal Imido Ligand
- Source :
- Inorganic Chemistry; 20210101, Issue: Preprints
- Publication Year :
- 2021
-
Abstract
- Oxidation of the low-spin FeIVimido complex [{(tBupyrr)2py}Fe═NAd] (1) ((tBupyrr)2py2–= 2,6-bis(3,5-di-tert-butyl-pyrrolyl)pyridine, Ad = 1-adamantyl) with AgOAc or AgNO3promotes reductive N–N bond coupling of the former imido nitrogen with a pyrrole nitrogen to form the respective ferric hydrazido-like pincer complexes [{(tBupyrrNAd)(tBupyrr)py}Fe(κ2-X)] (X = OAc–, 2OAc; NO3–, 2NO3). Reduction of 2OAcwith KC8cleaves the N–N bond to reform the FeIVimido ligand in 1, whereas acid-mediated demetalation of 2OAcor 2NO3yields the free hydrazine ligand [(tBupyrrNHAd)(tBupyrrH)py] (3), the latter of which can be used as a direct entry to the iron imido complex when treated with [Fe{N(SiMe3)2}2]. In addition to characterizing these Fe systems, we show how this nitrene transfer strategy can be expanded to Co for the one-step synthesis of Co{(tBu-NHAdpyrr)(tBupyrr)py}] (4) ((tBu-NHAdpyrr)(tBupyrr)py2–= 2-(3-tBu-5-(1-adamantylmethyl-2-methylpropane-2-yl)-pyrrol-2-yl)-6-(3,5-tBu2-pyrrol-2-yl)-pyridine).
Details
- Language :
- English
- ISSN :
- 00201669 and 1520510X
- Issue :
- Preprints
- Database :
- Supplemental Index
- Journal :
- Inorganic Chemistry
- Publication Type :
- Periodical
- Accession number :
- ejs57393550
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.1c01509