The Bicyclic Structure of a Novel TMEDA-Solvated Lithium Chloride Tetramer [(LiCl)4.cntdot.3.5TMEDA]2: X-ray Structural Analysis and MO Investigations

Fortuitous formation of [(LiCl)6{(Me2NCH2C8H5N)3P}2]: an amine-ligated hexameric lithium chloride aggregate

“…Li-N distances (avg. 2.089 Å ) are comparable to those observed for TMEDA complexes of LiCl aggregates [11,12]. The metric parameters for the phosphine are normal.…”

“…Many simple lithium chloride aggregates, such as [(LiCl) 4 (HMPTA) 4 ] [6], [(LiCl) 4 (Et 2 O) 4 ] [7], [(LiCl) 2 (THF) 4 ] [8], [LiCl AE THF] 1 [9], and [(LiCl) 4 (azetidine) 2 {N-(3-aminopropyl)azetidine} 2 ] [10], were obtained from reaction mixtures serendipitously. Many cannot be produced by direct reactions of lithium chloride with bulk solvent or ligand [11,12].…”

“…The core can be described as two Li 3 Cl 3 hexagons of alternating lithium and chlorine atoms linked by Li-Cl interactions to form four-member rings along the edge of the drum, a common motif for compounds of many main group elements [22], but one unprecedented for aggregates of lithium halides. [6][7][8][9][10][11][12].…”

From Aryl Bromides to Enantioenriched Benzylic Alcohols in a Single Flask: Catalytic Asymmetric Arylation of Aldehydes

“…In contrast, the lithium salts likely have at least two available coordination sites. Structures of [tmeda⋅LiCl] n (TMEDA = N , N , N ′, N ′‐tetramethylethylene diamine) contain four‐coordinate lithium centers with bridging chlorides 18. 19 Furthermore, we expected that the zinc catalyst is more sterically saturated than the lithium salts.…”

Assessment of the LiX salt-effect in anthracenyl lithiums

“…In C-C-bond formation reactions of organolithiums with alkyl or aryl halides lithium halides are formed in equimolar amounts and it might be energetically and stereochemically advantageous if the LiX reaction product is already preorganized in the starting material. 13 In this light we revisited the R m Li m+n X n complexes to shed some light on their aggregation and possibly redirect the perception of mixed aggregates regarding their synthetic potential, rather than just discharging them as problematic side effects.…”