Synthesis and Characterization of Two "Tied-Back" Lithium Ketimides and Isolation of a Ketimide-Bridged [Cr2]6+ Dimer with Strong Antiferromagnetic Coupling.

Abstract

Reaction of 1 equiv of KN(SiMe3)2 with 9-fluorenone results in the formation of (Me3Si)N═C13H8 (1) in high yield after work-up. Addition of 1 equiv of phenol to 1 results in rapid desilylation and formation of 9-fluorenone imine, HN═C13H8 (2). Subsequent reaction of 2 with 1 equiv of LiNiPr2 results in deprotonation and formation of [Li(Et2O)]4[N═C13H8]4 (3) in good yield. Reaction of 1 equiv of KN(SiMe3)2 with 2-adamantanone for 7 days at room temperature results in the formation of (Me3Si)N═C10H14 (4) in good yield. Dissolution of 4 in neat MeOH results in rapid desilylation concomitant with formation of 2-adamantanone imine, HN═C10H14 (5). Subsequent reaction of 5 with 1 equiv of LiNiPr2 results in formation of [Li(THF)]4[N═C10H14]4 (6). Both 3 and 6 were characterized by X-ray crystallography. Finally, reaction of CrCl3 with 3.5 equiv of 6 results in formation of the [Cr2]6+ dimer, [Li][Cr2(N═C10H14)7] (7), which can be isolated in modest yield after work-up. Complex 7 features 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.