Cationic aza-macrocyclic complexes of germanium(ii) and silicon(iv)

Everett, Matthew, Jolleys, Andrew, Levason, William, Light, Mark E., Pugh, David and Reid, Gillian (2015) Cationic aza-macrocyclic complexes of germanium(ii) and silicon(iv). Dalton Transactions, 44 (48), 20898-20905. (doi:10.1039/c5dt03941j).

Abstract

[GeCl2(dioxane)] reacts with the neutral aza-macrocyclic ligands L, L = Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane), Me4cyclen (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) or Me4cyclam (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(Me3tacn)]Cl2 and [Ge(Me3tacn)]Cl[O3SCF3] were also isolated; the preparation of [Ge(Me4cyclen)][GeCl3]2 is also described. The structures of the Me3tacn complexes show ?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(Me4cyclen)][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(Me3tacn)]Y (Y = O3SCF3, BArF; [B{3,5-(CF3)2C6H3}4]) and [SiHCl2(Me3tacn)][BArF], obtained from reaction of SiCl4 or SiHCl3 with Me3tacn, followed by addition of either Me3SiO3SCF3 or Na[BArF], contain distorted octahedral cations, with facial ?3-coordinated Me3tacn. The open-chain triamine, Me2NCH2CH2N(Me)CH2CH2NMe2 (pmdta), forms [SiCl3(pmdta)][BArF] and [SiBr3(pmdta)][BArF] under similar conditions, containing mer-octahedral cations.

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Contributors

Author: William Levason

Author: Mark E. Light

Author: Gillian Reid

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