Imide transfer properties and reactions of the magnesium imide ((THF)MgNPh)(6): A versatile synthetic reagent

Imide transfer properties of ((THF)MgNPh)(6) (1) and the synthesis of the related species {(THF)MgN(1-naphthyl)}(6) . 2.25THF (2), via the reaction of dibutylmagnesium with H2N(1-naphthyl), in a THF/heptane mixture are described. Treatment of 1 with Ph(2)CO, 4-Me(2)NC(6)H(4)NO, t-BuNBr(2) (3), PCl3, or MesPCl(2) (Mes = 2,4,6-Me(3)C(6)H(2)-)leads to the isolation of Ph(2)CNPh (4), 4-Me(2)NC(6)H(4)NNPh (5), t-BuNNPh (6), (PhNPCl)(2), (7), or (MesPNPh)(2) (8) in moderate yield. Reaction between 1 and GeCl2 . dioxane, SnCl2, or PbCl2 affords the M(4)N(4) (M = Ge, Sn, Pb) cubane imide derivative (GeNPh)(4) (9), [(SnNPh)(4) (MgCl2(THF)(4))](infinity) (10), (SnNPh)(4) . 0.5PhMe (11), or (PbNPh)(4) . 0.5PhMe (12). Interaction of 1 with Ph(3)PO, (Me(2)N)(3)PO, or Ph(2)SO furnishes the complex (Ph(3)POMgNPh)(6) (13), {(Me(2)N)(3)POMgNPh}(6) . 2PhMe (14), or (Ph(3)SOMgNPh)(6) (15). The addition of 3 equiv of MgBr2 to 1 gives 1.5 equiv of ((THF)Mg)(6)(NPh)(4)Br-4 (16) in quantitative yield, whereas treatment of 16 with 4 equiv of 1,4-dioxane is an alternative synthetic route to 1. Compounds 2, 3, 9, 10, and 14 were characterized by X-ray crystallography. The reactions demonstrate that 1 is a versatile and useful reagent for the synthesis of a variety of main group imides. Crystal data at 130 K with Mo K alpha (lambda = 0.710 73 Angstrom) radiation for 3 or Cu K alpha (lambda = 1.541 78 Angstrom) radiation for 2, 9, 10, and 14: 2, C93H108Mg6N6O7.25, a = 28.101(7) Angstrom, b = 35.851(7) Angstrom, c = 36.816(7) Angstrom, Z = 2, space group Fddd, R = 0.068 for 3500 (I > 2 sigma(I)) data; 3, C4H9Br2N, a = 6.682(2) Angstrom, b = 10.834(3) Angstrom, c = 11.080(3) Angstrom, alpha = 66.25(2)degrees, beta = 89.88(2)degrees, gamma : 82.53(2)degrees, Z = 4, space group <P(1)over bar>, R = 0.038 for 2043 (I > 2 sigma(I)) data; 9, C24H20Ge4N4, a = 10.749(2) Angstrom, b = 12.358(3) Angstrom, c 35.818(7) Angstrom, Z = 8, space group Pbca, R = 0.040 for 2981 (I > 2 sigma(I)) data; 10, C40H52Cl2MgN4O4Sn4, a = 12.770(3) Alpha, b = 13.554(3) Angstrom, c = 25.839(5) Angstrom, Z = 4, space group P2(1)2(1)2(1), R = 0.040 for (I > 2 sigma(I)) data; 14, C86H154. Mg6N4O6P6, a = 22.478(4) Angstrom, b = 16.339(3) Angstrom, c = 29.387(6) Angstrom, Z = 4, space group Pbcn, R = 0.081 for 4696 (I > 2 sigma(I)) data.