Die SiP‐Bindung in Me3SiPPh2 wird von den Heteroallenen CS2, RNCS (R  Ph, Me) und RNCO (R  Ph, Me) leicht elektrophil angegriffen. Es entstehen die in der Regel luft‐ und feuchtigkeitsempfindlichen 1:1‐Insertionsprodukte mit SiS‐ (CS2) bzw. SiN‐Bindung (RNCS, RNCO) neben geringen Mengen Hydrolyseprodukten. Die IR‐, 1H‐NMR‐ und Massenspektren werden diskutiert.

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Abstract The phosphinothioformimidato complex (1) crystallizes triclinic in the space group P1̄ with lattice constants a = 989.4(9) pm, b - 1042.0(8) pm, c = 1088.5(8) pm, α = 91.45(4)°, β = 97.10(4)°, γ = 100.53(5)°. The four-membered chelate ring is folded over the P-S edge by a dihedral angle of 167.1°. The crystal system of the thiophosphoryl thioformimidato complex (2) is monoclinic with the space group P21/c, and the lattice parameters are a = 1109.5(3) pm, b = 966.0(3) pm, c = 2256.7(3) pm, β=103.11(2)°. The chelate ligand is linked to the metal by two S atoms forming a five-membered ring in the “envelope” conformation with the thiophosphoryl S atom at the apical position.