Cationic aza-macrocyclic complexes of germanium(II) and silicon(IV)

[GeCl2(dioxane)] reacts with the neutral aza-macrocyclic ligands L, L = Me(3)tacn (1,4,7-trimethyl-1,4,7-tri-azacyclononane), Me(4)cyclen (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) or Me(4)cyclam (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and two mol. equiv. of Me3SiO3SCF3 in thf solution to yield the unusual and hydrolytically very sensitive [Ge(L)][O3SCF3](2) as white solids in moderate yield. Using shorter reaction times [Ge(Me(3)tacn)]Cl-2 and [Ge(Me(3)tacn)]Cl[O3SCF3] were also isolated; the preparation of [Ge(Me(4)cyclen)][GeCl3](2) is also described. The structures of the Me(3)tacn complexes show kappa(3)-coordination of the macrocycle, with the anions interacting only weakly to produce very distorted five- or six-coordination at germanium. In contrast, the structure of [Ge(Me(4)cyclen)][O3SCF3](2) shows no anion interactions, and a distorted square planar geometry at germanium from coordination to the tetra-aza macrocycle. Crystal structures of the Si(IV) complexes, [SiCl3(Me(3)tacn)] Y (Y = O3SCF3, BArF; [B{3,5(CF3)(2)C6H3}(4)]) and [SiHCl2(Me(3)tacn)][BArF], obtained from reaction of SiCl4 or SiHCl3 with Me(3)tacn, followed by addition of either Me3SiO3SCF3 or Na[BArF], contain distorted octahedral cations, with facial. 3-coordinated Me(3)tacn. The open-chain triamine, Me2NCH2CH2N(Me)CH2CH2NMe2 (pmdta), forms [SiCl3(pmdta)][BArF] and [SiBr3(pmdta)][BArF] under similar conditions, containing mer-octahedral cations.