Abstract: | The first zwitterionic borata‐bis(NHC)‐stabilized phosphaketenyl germyliumylidene (L2(O=C=P)Ge:] 2 (L2=(p ‐tolyl)2B1‐(1‐adamantyl)‐3‐yl‐2‐ylidene]2) has been synthesized by salt‐metathesis reaction of L2(Cl)Ge:] 1 with sodium phosphaethynolate (dioxane)n NaOCP]. Unexpectedly, its exposure to UV light affords, after reductive elimination of the entire PCO group, the unprecedented L2Ge‐GeL2] complex 3 in 54 % yields bearing the Ge22+ ion with Ge in the oxidation state +1. In addition, the 1,3‐digermylium‐2,4‐diphosphacyclobutadiene L2Ge(μ‐P)2GeL2] 4 and bis(germyliumylidenyl)‐substituted diphosphene (L2Ge‐P=P‐GeL2)] 5 could also be obtained in moderate yields. The formation of 3 – 5 and their electronic structures have been elucidated with DFT calculations. |