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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

Authors :
Kent, Greggory T.
Cook, Andrew W.
Damon, Peter L.
Lewis, Richard A.
Wu, Guang
Hayton, Trevor W.
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