Abstract
Insertion of dichlorogermylene (from GcCl2-dioxane) into the P-P bonds of tetraalkyldiphosphanes ((PRR)2 (2a: R, R ˭ i-Pr; 2b: R˭ t-Bu, R˭i-Pr; 2C; R, R, ˭t-Bu) leads 10 dichlorobis(dialkylphosphanyl)germanes 3a-c. With 2a. the insertion remains incomplete: 38 exists in an equilibrium with an adduct of diphosphane 2a with GeCI2, Subsequently 3b and 3c undergo a-climinarions to dialkylchlorophosphanes Sb and Sc and the dimeric phosphanylgermylenes (RR PGeGl)2 4b and 4c [1]. Similar to the above (but in absence of dioxane), reacting the richlorogcrmylphosphane i-Pr(t-Bu)PGeCL3, 7c [2] with the related trichlorosilylphosphanc i-Pr(t-Bu)PSiCl3 provided a mixture of SiCl4, 1c, 3c, 5c and 7c, 3a and 3c have been trapped as inert molybdenum complexes (CO)4 MO(μ-PRR)2 GeGl2 6a and 6c from cquilibrilia conraining la/ 2a/ 3a and 3c/ 4c / 5c / 7c respectively.