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By Alan R. Katritzky (Eds.)

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Extra info for Aminomethylenemalonates and Their Use in Heterocyclic Synthesis

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While Et2 O and Me2 S in [(Et2 O)LiPh]4 [43] and [(Me2 S)LiPh]4 [44] coordinate the apical lithium atoms in the tetrahedral tetramers, addition of the chelating diamine TMEDA results in the formation of the dimer [(tmeda)LiPh]2 [41] (30). 2). Consequently, on addition of donor bases or implementation of donating side arms it is the π-bonding that is given up first [3]. In the dimer of [(Et2 O)t-BuLi]2 [2a] (31) and [LiC(SiMe)3 ]2 [42] (32), the (LiC)2 four-membered ring is also present but the bulky organic groups provide shielding.

As in the alkali-metal magnesiates, the outcome of these reactions is strongly influenced by the donor base ligand. 8. 8 Different aggregates of alkali-metal zincate complexes. In the ion-contacted zincate [(tmeda)2 Li2 ZnMe4 ] [51] (44), two TMEDA coordinated lithium cations bind to the tetrahedral [ZnMe4 ]2− anion, forming two orthogonally fused heterobimetallic four-membered rings. In the presence of the tridentate chelating ligand PMDETA, the contact ion pair [(pmdeta)LiMe2 ZnMe] [52] (45) with lithium and zinc atoms bridged by two methyl groups was obtained.

2 Asymmetric Aggregates of [Me3 SiCH2 Li] (4) In 2010, Stalke et al. 10). As in the alkyllithium compounds, the structural key feature is the distorted tetrahedral lithium core with averaged Li⋅⋅⋅Li distance of 256 pm, which is shorter than those in [Me3 SiCH2 Li]6 but longer than those in 9–14. 10 Solid-state structures of the asymmetric tetramers [(Et2 O)2 (LiCH2 SiMe3 )4 ] (15) (a) and [(t-BuOMe)2 (LiCH2 SiMe3 )4 ] (16) (b). 4 Selected bond lengths in the asymmetric tetramers 15 and 16 (pm).

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