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Imide Transfer Properties and Reactions of the Magnesium Imide ((THF)MgNPh) 6 : A Versatile Synthetic Reagent

1996; American Chemical Society; Volume: 35; Issue: 11 Linguagem: Inglês

10.1021/ic951510a

1520-510X

Warren J. Grigsby, T. Hascall, Jeffrey J. Ellison, Marilyn M. Olmstead, Philip P. Power,

Organometallic Complex Synthesis and Catalysis

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 H(2)N(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), PCl(3), 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 GeCl(2).dioxane, SnCl(2), or PbCl(2) affords the M(4)N(4) (M = Ge, Sn, Pb) cubane imide derivative (GeNPh)(4) (9), [(SnNPh)(4).{MgCl(2)(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(2)SOMgNPh)(6) (15). The addition of 3 equiv of MgBr(2) 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 Kalpha (lambda = 0.710 73 Å) radiation for 3 or Cu Kalpha (lambda = 1.541 78 Å) radiation for 2, 9, 10, and 14: 2, C(93)H(108)Mg(6)N(6)O(7.25), a = 28.101(7) Å, b = 35.851(7) Å, c = 36.816(7) Å, Z = 2, space group Fddd, R = 0.068 for 3500 (I > 2sigma(I)) data; 3, C(4)H(9)Br(2)N, a = 6.682(2) Å, b = 10.834(3) Å, c = 11.080(3) Å, alpha = 66.25(2) degrees, beta = 89.88(2) degrees, gamma = 82.53(2) degrees, Z = 4, space group P&onemacr;, R = 0.038 for 2043 (I > 2sigma(I)) data; 9, C(24)H(20)Ge(4)N(4), a = 10.749(2) Å, b = 12.358(3) Å, c = 35.818(7) Å, Z = 8, space group Pbca, R = 0.040 for 2981 (I > 2sigma(I)) data; 10, C(40)H(52)Cl(2)MgN(4)O(4)Sn(4), a = 12.770(3) Å, b = 13.554(3) Å, c = 25.839(5) Å, Z = 4, space group P2(1)2(1)2(1), R = 0.040 for (I > 2sigma(I)) data; 14, C(86)H(154)Mg(6)N(4)O(6)P(6), a = 22.478(4) Å, b = 16.339(3) Å, c = 29.387(6) Å, Z = 4, space group Pbcn, R = 0.081 for 4696 (I >2sigma(I)) data.