Synthesis and structures of crystalline dilithium diamides and aminolithium amides derived from N,N′-disubstituted 1,2-diaminobenzenes or 1,8-diaminonaphthalene

The crystalline dilithium diamides [Li-2(mu -A)](2) 1, [Li(mu -A){mu -Li( thf)(mu -thf)}](2) 2, [Li( thf)(2)(mu -A) Li( thf)] 3, mu[{Li(tmen)}(2)(mu -A)] 4, [{Li(mu -A')(thf)(2)}(mu -Li)] (2) 5, [{Li(tmen)}(2)(mu -A ")] 6, [{Li(mu -B')(thf)}(mu -Li)] (2) 7, [{Li( tmen)} (2) {mu -NSi(Me)(2) C10H6N-1,8}] 9 and[{Li(tmen)}(2)(mu -B)] 13 and aminolithium amides [Li{(mu -NC10H6NH-1,8)SiMe2}(OEt2)] (2) 8, [Li(tmen)(2){NSi(Me)(2)C10H6NH-1,8}]12 and [Li(tmen){mu -NSi( Me)(2)C10H6NH-1,8}] 15 have been prepared from the appropriate H-2(A), H-2(A'), H-2(A "), H-2(B') or H-2(B) [A=1,2-{N(SiMe3)}(2)C6H4, A'=1,2-{N(CH2But)}(2)C6H4, A " =1,2-{N(SiMe2CH=CH2)}(2)C6H4, B=1,8-{N(SiMe3)}(2)C10H6 and B'=1,8-{N(CH2But)}(2)C10H6], LiBun and (except for 1) the chosen neutral coligand (thf, tmen or Et2O). The X-ray structures of 1-8 are presented and further evidence for 9 and 13 is provided by converting them into derivatives: Me2Si{N(R')C10H6NR'-1,8} (R'=Me 10 or H 11) from 9 and [Zr(eta (5)-C5H5)(2)(B)] 14 from 13. The formation, from H-2 (B) and LiBun under appropriate and mild conditions, of N-lithio- or dilithio-derivatives 8, 12 and 15 of the tricyclic anions [1,8-{NSi(Me)(2)C10H6NH}](-) or [1,8-{NSi(Me)(2)C10H6N}](2-) is especially noteworthy.