The crystalline compounds [Hg{N(R)C(H)NR}(2)] (1), [Fe(L)(2)](2) (2), [Ce(L)(2)Cl](2) (3), [(AlMe2)(3){(N(R)C(H)NC(H)N)(2)C(H)NC(H)NR}] (4), and [Ag8Na{(N(R)C(H)N)(2)(C(H)N)(4)R}(3)](5) were obtained from [Li(L)](3) (A) (for 1) or[Na(L)](3) (B) and HgCl2, FeBr2, CeCl3, Al(Cl)Me-2, and AgOTf, respectively [L = N(R){C(H)N}(3)R; R = SiMe3]. Compounds 1, 2, 3, and 5 were prepared in tetrahydrofuran (THF) at 20 degrees C; for 4, it was C6H14 at -78 degrees C. NMR data for 1 showed only a single SiMe3 environment for 1, implicating a fast exchange process. Single crystal X-ray data showed dinuclear structures for 2 and 3. Each ligand [L](-) in crystalline 2 was bound to each of the two Fe atoms in a kappa(1)- or kappa(2)-fashion, respectively, with one NSiMe3 group of the former unattached; this was consistent with VT H-1 NMR spectral data indicative of fast exchange (at 313 K) between axial kappa(1)- and equatodal kappa(2)-N,N-coordination to Fe. The magnetic moment for 2 in C6H6 was appropriate for high-spin octahedral Fe(II). The ligands [L](-) in crystalline 3 are arranged in a helical fashion. The NMR spectra of 4 in C6D5CD3 showed that there is an equilibrium between two asymmetric structures; minor co-products were 4', assigned as a symmetrical isomer of 4, and N(R)C(H)NR2. The anion of 5 is proposed to be identical to that of 4'. Routes to the ligands of 1, 4, 4', and 5 are suggested; the key feature is that the ligand [L](-), unless tethered in an appropriate metal-containing matrix (as in A, B, 2, or 3), is labile because of SiMe3 mobility, fragmentation, and/or recombination.