Investigations into Cationic Polyether Complexes of Germanium(II) and Tin(II)

Previously, crown ethers were demonstrated to be excellent ligands in the stabilization of naked Ge(II) dications. As an extension of this work, the reactivity of these complexes with small molecules was investigated. Herein, it is reported that the addition of one equivalent of water or ammonia to [Ge[15]crown-5][OTf]2 produces the stable complexes [Ge[15]crown-5-H2O][OTf]2 and [Ge[15]crown-5-NH3][OTf]2, respectively. The synthetic potential of these complexes is also described, investigating their deprotonated variants in pursuit of unsaturated Ge compounds, as well as their alcohol and amine analogues. The interaction of [Ge[15]crown-5][OTf]2 with heavier element hydrides was also studied. Unlike the aforementioned donor-acceptor complexes, the room temperature addition of H2S and PH3 results in the precipitation of GeS and GeP, respectively. Lastly, the suitability of glymes in the stabilization of Ge(II) and Sn(II) salts was confirmed. Both triglyme and tetraglyme complexes were isolated and structurally characterized, some with unexpected results