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

The synthesis of the 2,4-bis(amino)cyclodiphosph(V)azane cis-[tBu(H)N(OPNtBu)2N(H)tBu] (3) and the syntheses and solid-state structures of cis-[Ph(H)N(EPNtBu)2N(H)Ph]
(E = S (6), Se (7)) are reported. When 6 was treated with nBuLi, the dilithio salt {[(2THF·LiPhN)(SPNtBu)2(NPhLi·2THF)]·THF} (10) was isolated. The reactions of cis-[tBu(H)N(E=PNtBu)2N(H)tBu (E = O (3), S (4), Se (5)) and cis-[R(H)N(ArPNtBu)2N(H)R] (R = tBu,
Ar = Ph (8), Ar = p-Tol (9)) with 2 equiv of trimethylaluminum afforded the bis(dimethylaluminum) complexes {(Me2Al)[RN(EPNtBu)2NR](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 η2-fashion, as dimeric aminophosphoranates.