The tetracyclic dilithio-Si,Si′-oxo-bridged bis(N,N′-methylsilyl-β-diketiminates) 2 and 3, having an outer macrocycle, were prepared from [Li{CH(SiMe3)SiMe(OMe)2}]∞ and 2 PhCN. They differ in that the substituent at the β-C atom of each diketiminato ligand is either SiMe3 (2) or H (3). Each of 2 and 3 has (i) a central Si–O–Si unit, (ii) an Si(Me) fragment N,N′-intramolecularly bridging each β-diketiminate, and (iii) an Li(thf)2 moiety N,N′-intermolecularly bridging the two β-diketiminates (thf = tetrahydrofuran). Treatment of [Li{CH(SiMe3)(SiMe2OMe)}]8 with 2Me2C(CN)2 yielded the amorphous [Li{Si(Me)2((NCR)2CH)}]n [R = C(Me)2CN] (4). From [Li{N(SiMe3)C(But)C(H)SiMe3}]2 (A) and 1,3- or 1,4-C6H4(CN)2, with no apparent synergy between the two CN groups, the product was the appropriate (µ-C6H4)-bis(lithium β-diketiminate) 6 or 7. Reaction of [Li{N(SiMe3)C(Ph)C(H)SiMe3}(tmeda)] and 1,3-C6H4(CN)2 afforded 1,3-C6H4(X)X′ (X = ; X′ = (9). Interaction of A and 2[1,2-C6H4(CN)2] gave the bis(lithio-isoindoline) derivative (5). The X-ray structures of 2, 3, 5 and 9 are presented, and reaction pathways for each reaction are suggested.