Rearrangement of a Ge(II) aryloxide to yield a new Ge(II) oxo-cluster [Ge 6 (μ 3 -O) 4 (μ 2 -OC 6 H 2 -2,4,6-Cy 3 ) 4 ](NH 3 ) 0.5 : main group aryloxides of Ge(II), Sn(II), and Pb(II) [M(OC 6 H 2 -2,4,6-Cy 3 ) 2 ] 2 (Cy = cyclohexyl).

The new Ge(II) cluster [Ge 6 (μ 3 -O) 4 (μ 2 -OC 6 H 2 -2,4,6-Cy 3 ) 4 ](NH 3 ) 0.5 (1) and three divalent Group 14 aryloxide derivatives [Ge(OC 6 H 2 -2,4,6-Cy 3 ) 2 ] 2 (2), [Sn(OC 6 H 2 -2,4,6-Cy 3 ) 2 ] 2 (3), and [Pb(OC 6 H 2 -2,4,6-Cy 3 ) 2 ] 2 (4) of the new tricyclohexylphenyloxo ligand, [(-OC 6 H 2 -2,4,6-Cy 3 ) 2 ] 2 (Cy = cyclohexyl), were synthesized and characterized. Complexes 1-4 were obtained by reaction of the metal bissilylamides M(N(SiMe 3 ) 2 ) 2 (M = Ge, Sn, Pb) with 2,4,6-tricyclohexylphenol in hexane at room temperature. If the freshly generated reaction mixture for the synthesis of 2 is stirred in solution for 12 h at room temperature, the cluster [Ge 6 (μ 3 -O) 4 (μ 2 -OC 6 H 2 -2,4,6-Cy 3 ) 4 ](NH 3 ) 0.5 (1), which features a rare Ge 6 O 8 core that includes ammonia molecules in non-coordinating positions, is formed. Complexes 3 and 4 were also characterized via 119 Sn{ 1 H} NMR and 207 Pb NMR spectroscopy and feature signals at -280.3 ppm ( 119 Sn{ 1 H}, 25 °C) and 1541.0 ppm ( 207 Pb, 37 °C), respectively. The spectroscopic characterization of 3 and 4 extends known 119 Sn parameters for dimeric Sn(II) aryloxides, but data for 207 Pb NMR spectra for Pb(II) aryloxides are rare. We present also a rare VT-NMR study of a homoleptic 3-coordinate Pb(II) aryloxide. The crystal structures of 2, 3, and 4 feature interligand H⋯H contacts that are similar in number to those of related transition metal derivatives despite the larger size of the group 14 elements.