Reversible and Irreversible [2+2] Cycloaddition Reactions of Heteroallenes to a Gallaphosphene.

[2+2] Cycloaddition reactions of gallaphosphene L(Cl)GaPGaL 1 (L=HC[C(Me)N(2,6-i-Pr2 C6 H3 )]2 ) with carbodiimides [C(NR)2 ; R=i-Pr, Cy] and isocyanates [RNCO; R=Et, i-Pr, Cy] yielded four-membered metallaheterocycles LGa(Cl)P[μ-C(X)NR]GaL (X=NR, R=i-Pr 2, Cy 3; X=O, R=Et 4, i-Pr 5, Cy 6). Compounds 4-6 reversibly react with CO2 via [2+2] cycloaddition at ambient temperature to the six-membered metallaheterocycles LGa(Cl)P[μ-C(O)O]-μ-C(O)N(R)GaL (R=Et 7, i-Pr 8, Cy 9). Compounds 2-9 were characterized by IR and heteronuclear (1 H, 13 C{1 H}, 31 P{1 H}) NMR spectroscopy and elemental analysis, while quantum chemical calculations provided a deeper understanding on the energetics of the reactions.