Organometallic polymers assembled from cation-p interactions: Use of ferrocene as a ditopic linker within the homologous series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

Addition of ferrocene to solutions of alkali metal hexamethyldisilazides M(HMDS) in arenes (in which M=Na, K, Rb, Cs) allows the subsequent crystallization of the homologous series of compounds [{(Me3Si)2NM}2 (Cp2Fe)]∞ (1–4). Similar reactions using LiHMDS led to the recrystallization of the starting materials. The crystal structures of 1–4 reveal the formation of one-dimensional chains composed of dimeric [{M(HMDS)}2] aggregates, which are bridged through neutral ferrocene molecules by η5-cation–π interactions. In addition, compounds 3 and 4 also contain interchain agostic MC interactions, producing two-dimensional 44-nets. Whereas 1 and 2 were prepared from toluene, the syntheses of 3 and 4 required the use of tert-butylbenzene as the reaction media. The attempted crystallization of 3 and 4 from toluene resulted in formation of the mixed toluene/ferrocene solvated complexes [{(Me3Si)2NM)2}2 (Cp2Fe)x(Tol)y]∞ (in which M=Rb, x=0.6, y=0.8, 5; M=Cs, x=0.5, y=1, 6). The extended solid-state structures of 5 and 6 are closely related to the 44-sheets 3 and 4, but are now assembled from a combination of cation–π, agostic, and π–π interactions. The charge-separated complex [K{(C6H6)2Cr}1.5(Mes)][Mg(HMDS)3] (15) was also structurally characterized and found to adopt an anionic two-dimensional 63-network through doubly η3-coordinated bis(benzene)chromium molecules. DFT calculations at the B3 LYP/6–31G* level of theory indicate that the binding energies of both ferrocene and toluene to the M(HMDS) dimers increases in the sequence Li<Na<K. This pattern is a consequence of the larger metals allowing more open coordination spheres to support cation–π contacts. By comparison, binding of the isolated metal cations to the aromatic groups follow the reverse order K<Na<Li. A combined analysis of theoretical and experimental data suggest that ferrocene is a stronger cation–π donor than toluene for the lighter metals, but that this difference is eliminated on descending the group.