The reaction of (Et3P)(2)PtGe[N(SiMe3)(2)](2) (1) with nitrosobenzene and 2-nitrosobenzene yields (Et3P)(2)-PtN(Ph)OGe[N(SiMe3)(2)](2) (3a) and (Et3P)(2)PgN(o-Tol)OGe[N(SiMe3)(2)](2) (3b), respectively. The reactivity of 3a with SO2, H2CO, CO2, and PhNCO was explored yielding the five-membered heterocyclic complex (Ee(3)P)(2)PtOC(H)(2)N(Ph)-PtS(O)(2)N(Ph)OGe[N(siMe(3))(2)](2) (6a) and the six-membered heterocyclic complexes (Et3P)(2)PtOC(H)(2)N(Ph)-OGe[N(SiMe3)(2)](2) (7a), (Et3P)(2)PtOC(O)N(Ph)OGe[N(SiMe3)(2)](2) (8a), and (Et3P)(2)PtN(Ph)C(O)N(Ph)OGe-[N(SiMe3)(2)](2) (9a), respectively. The structures of 3a, 6a, 7a, and 9a were determined by single-crystal X-ray diffraction. 3b was observed to react in a fashion similar to 3a as demonstrated by reactions with SO2 and H2CO which gave (Et3P)(2)PtS(O)(2)N(o-Tol)OGe[N(SiMe3)(2)](2) (6b) and (Et3P)(2)PtOC(H)(2)N(o-Tol)OGe [N(SiMe3)(2)](2) (7b). Complexes 6a and 6b represent the first isolated and characterized examples of metal-stabilized-S(O)(2)N-(R)O- fragments, the isoelectronic analogue of an elusive intermediate proposed as the first step in Contact Process for the oxidation of SO2 by platinum catalysts. As a group, the reactions in this paper demonstrate the cooperative ability of metal-germylenes to activate unsaturated organic substrates and promote their subsequent chemical modification, while avoiding scission of the Pt-Ge bond.