Stiba-, Arsa- and Phosphastannenes: Syntheses and Reactivities.

A facile synthesis for unprecedented stibastannene (10) featuring a Sn=Sb-double bond together with the homologous arsa- (9) and phosphastannenes (8) is presented. Chloride abstraction from respective stannyl pnictinidenes [E=P (5), As (6), Sb (7)], which were made accessible by reduction of ECl addition products at an intramolecular phosphine-stabilized stannylene, gave the pnictastannenes in moderate yields. The pnictastannenes coordinate Pd(PPh ) fragments (12-14) and the phosphastannene forms also a nickel coordination compound with the Ni(PPh ) -fragment (11). 2,3-Dimethylbutadiene shows a [2+4]-cycloaddition (15-17) in reaction with the pnictastannenes (8-10). Products of a [2+2]-addition (18, 19) were isolated as the phosphaalkyne reaction products for 8 and 9. Addition of an O-H bond at the Sn=P-bond was found in reaction of water with phosphastannene 8. Reaction with ammonia afforded the NH -adducts (21-23) at the tin atom for pnictastannenes 8-10. Only in the case of the arsastannene an azide reaction product featuring a three membered Sn-As-N-ring was obtained.