Synthesis and structures of lithium N-trimethylsilyl- and -neopentyl-anilides and their Et2O and tmen adducts; crystal structures of [(Li{μ-N(Ph)R}-trans)2(μ-tmen)]∞ (R = SiMe3 1 or CH2But 2) and [Li{μ-N(Ph)CH2But}(OEt2)]2 †

Treatment of N-trimethylsilyl- or -neopentyl-aniline successively with n-butyllithium and tmen in hexane yielded the crystalline polymeric lithium amides [(Li{μ-N(Ph)R}-trans)2(μ-tmen)]∞ (R = SiMe31 or CH2But2), which contain the rare bridging, rather than chelating, tmen ligands. Details are also provided of: (i) the preparation of crystalline [Li{N(Ph)SiMe3}]4, hydrocarbon-insoluble [Li{N(Ph)CH2But}]n, and diethyl ether adducts [Li{μ-N(Ph)R-trans}(OEt2)]2 (R = SiMe3 or CH2But); (ii) variable temperature multinuclear NMR spectra in toluene-d8 and (iii) three crystal structures.