New Reactivity Patterns in 3H-Phosphaallene Chemistry [Aryl-P=C=C(H)-tBu]: Hydroboration of the C=C Bond, Deprotonation and Trimerisation.

3H-Phosphaallenes, R-P=C=C(H)C-R' (3), are accessible in a multigram scale on a new and facile route and show a fascinating chemical reactivity. BH3 (SMe2 ) and 3 a (R=Mes*, R'=tBu) afforded by hydroboration of the C=C bonds of two phosphaallene molecules an unprecedented borane (7) with the B atom bound to two P=C double bonds. This compound represents a new FLP based on a B and two P atoms. The increased Lewis acidity of the B atom led to a different reaction course upon treatment of 3 a with H2 B-C6 F5 (SMe2 ). Hydroboration of a C=C bond of a first phosphaallene is followed in a typical FLP reaction by the coordination of a second phosphaallene molecule via B-C and P-B bond formation to yield a BP2 C2 heterocycle (8). Its B-P bond is short and the B-bound P atom has a planar surrounding. Treatment of 3 a with tBuLi resulted in deprotonation of the β-C atom of the phosphaallene (9). The Li atom is bound to the P atom as demonstrated by crystal structure determination, quantum chemical calculations and reactions with HCl, Cl-SiMe3 or Cl-PtBu2 . The thermally unstable phosphaallene Ph-P=C=C(H)-tBu gave a unique trimeric secondary product by P-P, P-C and C-C bond formation. It contains a P2 C4 heterocycle and was isolated as a W(CO)4 complex with two P atoms coordinated to W (15).