Trispirocyclic bis(dimethylaluminum)bis(amido) cyclodiphosph(V)azanes

The synthesis of the 2,4-bis(amino)cyclodiphosph(V)azane cis-[Bu-t(H)N(O=(PNBu)-Bu-t)(2)N(H)Bu-t] (3) and the syntheses and solid-state structures of cis- [Ph(H)N(E=(PNBu)-Bu-t)(2)N(H)Ph] (E = S (6), Se (7)) are reported. When 6 was treated with (BuLi)-Bu-n, the dilithio salt {[(2THF . LiPhN)(S=(PNBu)-Bu-t),(NPhLi . 2THF)]. THF) (10) was isolated. The reactions of cis-[Bu-t(H)N(E=(PNBu)-Bu-t)(2)N(H)Bu-t (E = O (3), S (4), Se (5)) and cis-[R(H)N(Ar=(PNBu)-Bu-t)(2)N(H)R] (R = Bu-t, Ar = Ph (8), Ar = p-Tol (9)) with 2 equiv of trimethylaluminum afforded the bis(dimethylaluminum) complexes {(Me2Al)[RN(E=(PNBu)-Bu-t)(2)NR](AlMe2)) (R = tBu, E = O (11), E = S (12), E = Se (13); R = Ph, E = S (14), Se (15), and R = tBu, E = N-p-Tol (16), E = N-Ph (17)). Compounds 11, 12, and 16 were characterized by single-crystal X-ray studies and shown to be trispirocyclic complexes in which the ligands coordinate both dimethylaluminum moieties in an eta (2)-fashion, as dimeric aminophosphoranates.