Varied reactions of [M(L)]3 with HgCl2, FeBr2, CeCl3, AgOTf; ligand transfer, nucleophilic attack with recombination and/or fragmentation [M = Li or Na; L = N(SiMe3){C(H)N}3SiMe3].
The crystalline compounds [Hg{N(R)C(H)NR}(2)] (1), [Fe(L)(2)](2) (2), [Ce(L)(2)Cl](2) (3), [(AlMe(2))(3){(N(R)C(H)NC(H)N)(2)C(H)NC(H)NR}] (4), and [Ag(8)Na{(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 HgCl(2), FeBr(2), CeCl(3), Al(Cl)Me(2), and AgOTf, respectively [L = N(R){C(H)N}(3)R; R = SiMe(3)]. Compounds 1, 2, 3, and 5 were prepared in tetrahydrofuran (THF) at 20 degrees C; for 4, it was C(6)H(14) at -78 degrees C. NMR data for 1 showed only a single SiMe(3) 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 NSiMe(3) group of the former unattached; this was consistent with VT (1)H NMR spectral data indicative of fast exchange (at 313 K) between axial kappa(1)- and equatorial kappa(2)-N,N'-coordination to Fe. The magnetic moment for 2 in C(6)H(6) 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 C(6)D(5)CD(3) 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)NR(2). 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 SiMe(3) mobility, fragmentation, and/or recombination.
Boesveld
W Marco
WM
Department of Chemistry, University of Sussex, Brighton BN1 9QJ, UK.
Hitchcock
Peter B
PB
Lappert
Michael F
MF