Abstract: | Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XX Formation and Structure of [{η2‐tBu2P–P}Pt(PHtBu2)(PPh3)] [{η2‐tBu2P1–P2}Pt(P3Ph3)(P4Ph3)] ( 2 ) reacts with tBu2PH exchanging only the P3Ph3 group to give [{η2‐tBu2P1–P2}Pt(P3HtBu2)(P4Ph3)] ( 1 ). The crystal stucture determination of 1 together with its 31P{1H} NMR data allow for an unequivocal assignment of the coupling constants in related Pt complexes. 1 crystallizes in the triclinic space group P1 (no. 2) with a = 1030.33(15), b = 1244.46(19), c = 1604.1(3) pm, α = 86.565(17)°, β = 80.344(18)°, γ = 74.729(17)°. |