The protonolysis reaction of the germanium(II) amide Ge[N(SiMe3)2]2 with calix[4]arene and calix[8]arene furnishes the two germanium(II) calixarene complexes {calix[4]}Ge2 and {calix[8]}Ge4, respectively, which have been crystallographically characterized. The calix[4]arene complex contains a Ge2O2 rhombus at the center of the molecule and is one of the only four germanium(II) calix[4]arenes that have been structurally characterized. The calix[8]arene species is the first reported germanium calix[8]arene complex, and it exhibits an overall bowl-shaped structure which contains two Ge2O2 fragments. The latter complex reacts with Fe2(CO)9 to yield an octairon compound, which has also been structurally characterized and contains four GeFe2 triangles arranged around the macrocyclic ring. The germanium(II) centers are oxidized to germanium(IV) in this process, with concomitant reduction of the neutral diiron species to Fe2(CO)(8)2- anions.

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The outcome of the reaction of the bulky metal(II) amides M[N(SiMe3)2]2. nTHF (M = Be, Zn, Ge, Sn, n = 0; M = Mg, Ca, n = 2) with (R)-3,3'-bis(trimethylsilyl)-1,1'-bi-2,2'-naphthol ((R)-1) or (S)-3,3'-bis(dimethylphenylsilyl)-1,1'-bi-2,2'-naphthol ((S)-9) depends on the identity of the metal and the nature of the 3,3'-substituents. When M = Be, Zn, or Ge, these amides serve as useful silylation agents that convert only one of the equivalent hydroxyl groups of the binaphthol (R)-1 to a trimethylsilyl ether, whereas the reactions of (R)-1 with the Mg, Ca, or Sn amides generate a polynuclear complex. The reaction pathway for these interconversions was qualitatively monitored using NMR ((1)H and (9)Be) spectroscopy. Treatment of Ge[N(SiMe3)2] 2 with (S)-9 yields both a silyl ether and the chelated germanium(II) binaphthoxide (S)-[Ge{O2C20H10(SiMe2Ph)2-3,3'}{NH3}], which was structurally characterized.