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Synthesis and Characterization of Two “Tied-Back” Lithium Ketimides and Isolation of a Ketimide-Bridged [Cr2]6+Dimer with Strong Antiferromagnetic Coupling
Synthesis and Characterization of Two “Tied-Back” Lithium Ketimides and Isolation of a Ketimide-Bridged [Cr2]6+Dimer with Strong Antiferromagnetic Coupling
- Source :
- Inorganic Chemistry; 20210101, Issue: Preprints
- Publication Year :
- 2021
-
Abstract
- Reaction of 1 equiv of KN(SiMe3)2with 9-fluorenone results in the formation of (Me3Si)N═C13H8(1) in high yield after work-up. Addition of 1 equiv of phenol to 1results in rapid desilylation and formation of 9-fluorenone imine, HN═C13H8(2). Subsequent reaction of 2with 1 equiv of LiNiPr2results in deprotonation and formation of [Li(Et2O)]4[N═C13H8]4(3) in good yield. Reaction of 1 equiv of KN(SiMe3)2with 2-adamantanone for 7 days at room temperature results in the formation of (Me3Si)N═C10H14(4) in good yield. Dissolution of 4in neat MeOH results in rapid desilylation concomitant with formation of 2-adamantanone imine, HN═C10H14(5). Subsequent reaction of 5with 1 equiv of LiNiPr2results in formation of [Li(THF)]4[N═C10H14]4(6). Both 3and 6were characterized by X-ray crystallography. Finally, reaction of CrCl3with 3.5 equiv of 6results in formation of the [Cr2]6+dimer, [Li][Cr2(N═C10H14)7] (7), which can be isolated in modest yield after work-up. Complex 7features a Cr–Cr bond length of 2.653(2) Å. Additionally, solid-state magnetic susceptibility measurements reveal strong antiferromagnetic coupling between the two Cr centers, with J= −200 cm–1.
Details
- Language :
- English
- ISSN :
- 00201669 and 1520510X
- Issue :
- Preprints
- Database :
- Supplemental Index
- Journal :
- Inorganic Chemistry
- Publication Type :
- Periodical
- Accession number :
- ejs55647703
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.1c00052