Mercury

Formation of Organolithium Hetero‐Aggregates [Li4Ar2(nBu)2] (Ar=C6H4CH(Me)NMe2‐2) during the Directed ortho‐Lithiation of [1‐(Dimethylamino)ethyl]benzene

“…[18, 23a-d] In this respect it is interesting to note that both b-carbon atoms of the two butyl groups are in close proximity to the same Li atom, that is, Li3. The observed overall structural geometry with a tetrahedral Li 4 core is similar to that observed in the hetero-aggregate {Li 4 [C 6 H 3 (CH(Et)NMe 2 ) 2 -2,6] 2 (nBu) 2 }, [19] but contrasts with the structures found for other [Li 4 (Aryl) 2 Bu 2 ] and [Li 4 -(Benz) 2 Bu 2 ] hetero-aggregates, [11,20,23] for which structures have been found in which the Li and bridging carbon atoms are present in a "ladder-type" arrangement.…”

“…[23] In this report, we reveal the formation of n-butyl aryl lithium hetero-aggregates during the DoM of [1-(dimethylamino)ethyl]benzene with nBuLi and detail the independent synthesis and structural characterization of these hetero-aggregates. With this information, we present unambiguous and compelling evidence for the intermediacy of aggregates of the type {[Li 4 Ar 2 Bu 2 ](Ar-H) 2 } as resting states in ortholithiation reactions of DMG-containing arenes. [7] Results and Discussion Synthesis: The treatment of a pentane solution of (R)-[1-(dimethylamino)ethyl]benzene with nBuLi in a 1:1 molar ratio afforded, after evaporation of the solvent, a pale yellow solid, (2 a: [Eq.…”

“…[1][2][3][4][5] In general, there are three primary synthetic routes to organolithium compounds: 1) direct metalation of an organic halide with Li metal, 2) halogen-Li exchange of an organic halide with a simple organolithium compound (typically nBuLi or tBuLi), and 3) deprotonation of a CH group from a suitable substrate with an alkyllithium compound. [1][2][3] This latter synthetic route is especially attractive because it is generally a very clean reaction, as the only products formed are the anticipated organolithium compound and an alkane. In this way, heteroatom-functionalized aromatic compounds can be easily lithiated selectively at the ortho position (i.e., "Directed ortho Metalation": DoM).…”

An organomercury enzyme activator as a versatile template for new organomercury(II) compounds encompassing homobimetallic (RHg/Hg) and heterobimetallic (RHg/Cd) compositions: Syntheses, photoluminescence and structures

“…Reactions of 1 with arylaldehyde and 1,5-diphenylthiocarbazone (dptc) were thoroughly investigated and, indeed, the structure of a (E)-acetyloxy Table 1 Crystal data and refinement details for compounds [1] Table 4 Selected bond lengths (Å) and angles (º) for [3] obtained by excitation at the respective absorption maxima (refer to Table 2). Fig.…”

“…The chemistry of organomercury compounds is one of the well-studied areas in organometallic chemistry and their co-ordination and structural aspects are also well documented [1][2]. The early development of organomercurial chemistry as compared to other organometallic compounds can be attributed to the high stability of organomercury compounds to air and moisture.…”