Ditetrelenes R2 E=ER2 (E=Si, Ge, Sn, Pb) substituted by multiple N/P/O/S-donor groups are extremely rare due to their propensity to disaggregate into their tetrylene monomers R2 E. We report the synthesis of the first fully phosphanyl-substituted digermene {(Mes)2 P}2 Ge=Ge{P(Mes)2 }2 (3, Mes=2,4,6-Me3 C6 H2 ), which adopts a highly unusual structure in the solid state, that is both strongly trans-bent and highly twisted. Variable-temperature 31 P{1 H} NMR spectroscopy suggests that 3 persists in solution, but is subject to a dynamic equilibrium between two conformations, which have different geometries about the Ge=Ge bond (twisted/non-twisted) due to a difference in the nature of their π-stacking interactions. Compound 3 undergoes unprecedented, spontaneous decomposition in solution to give a unique GeI cluster {(Mes)2 P}4 Ge4 ⋅5 CyMe (7).
Keywords: Cluster; Germanium; Multiple Bond; Phosphorus; Solid-State Structure.
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