Phosphane-functionalized heavier tetrylenes: synthesis of silylene- and germylene-decorated phosphanes and their reactions with Group 10 metal complexes.

ABSTRACT

The stable phosphane-functionalized heavier tetrylenes E(tBu2bzam)pyrmPtBu2 (E = Si (1Si), Ge (1Ge); tBu2bzam = N,N'-ditertbutylbenzamidinate; HpyrmPtBu2 = ditertbutyl(2-pyrrolylmethyl)phosphane) have been prepared by reacting the amidinatotetrylenes E(tBu2bzam)Cl (E = Si, Ge) with LipyrmPtBu2. The reactions of 1Si and 1Ge with selected M0 and MII (M = Ni, Pd, Pt) metal precursors have allowed the synthesis of square-planar [MCl2{κ2E,P-E(tBu2bzam)pyrmPtBu2}] (M = Ni, Pd, Pt; E = Si, Ge), tetrahedral [Ni{κ2E,P-E(tBu2bzam)pyrmPtBu2}(cod)] (E = Si, Ge; cod = 1,5-cyclooctadiene) and triangular [M{κ2E,P-E(tBu2bzam)pyrmPtBu2}(PPh3)] (M = Pd, Pt; E = Si, Ge) complexes, showing that 1Si and 1Ge are excellent Si,P- and Ge,P-chelating ligands that, due to their large steric bulk, are able to stabilize three-coordinate Pd0 and Pt0 complexes.