Four group 15 monochlorides of the type EAr(2)Cl [Ar = 2-[(dimethylamino)methyl]phenyl, 2-(Me(2)NCH(2))C(6)H(4) (C(9)H(12)N), E = Sb (4), E = Bi (5); Ar = 8-(dimethylamino)-1-naphthyl, 8-(Me(2)N)C(10)H(6) (C(12)H(12)N), E = Sb (6), E = Bi (7)] have been prepared via the salt elimination reactions of 2 equiv of either 2-(Me(2)NCH(2))C(6)H(4)Li or 8-(Me(2)N)C(10)H(6)Li with ECl(3). Four related group 15 dihalides of the type EArX(2) [Ar = 8-(Me(2)N)C(10)H(6), X = Cl, E = As, (8), E = Sb (9); Ar = 2-(Me(2)NCH(2))C(6)H(4), X = Cl, E = Bi (10); X = I, E = Bi (11)] have been prepared via the salt elimination reactions of equimolar amounts of 8-(Me(2)N)C(10)H(6)Li or 2-(Me(2)NCH(2))C(6)H(4)Li with EX(3). The X-ray crystal structures of 4-6, 8, 9, and 11 are described, and the observed trends in the degree of intramolecular coordination of the nitrogen atoms are consistent with the view that the Lewis acidity of these complexes is associated with the E-X sigma orbitals. Crystal data for 4: triclinic, space group P&onemacr;, a = 9.1483(1) Å, b = 9.4868(1) Å, c = 12.9776(2) Å, alpha = 70.614(8) degrees, beta = 85.738(9) degrees, gamma = 83.094(9) degrees, V = 1054.0(2) Å(3), Z = 2, R = 0.0420. Crystal data for 5: monoclinic, space group P2(1)/c, a = 11.9498(1) Å, b = 11.4695(1) Å, c = 13.9456(8) Å, beta = 104.536(6) degrees, V = 1850.2(3) Å(3), Z = 4, R = 0.0375. Crystal data for 6: monoclinic, space group P2(1)/n, a = 9.4991(8) Å, b = 23.455(4) Å, c = 9.726(1) Å, beta = 100.629(8) degrees, V = 2129.8(4) Å(3), Z = 4, R = 0.0406. Crystal data for 8: orthorhombic, space group P2(1)2(1)2(1), a = 9.713(3) Å, b = 9.835(4) Å, c = 13.310(3) Å, V = 1273.8(5) Å(3), Z = 4, R = 0.0695. Crystal data for 9: orthorhombic, space group P2(1)2(1)2(1), a = 9.7140(3) Å, b = 10.0196(1) Å, c = 13.444(3) Å, V = 1308.5(3) Å(3), Z = 4, R = 0.0320. Crystal data for 11: monoclinic, space group P2(1)/c, a = 7.9455(7) Å, b = 19.3949(3) Å, c = 8.6226(9) Å, beta = 93.338(9) degrees, V = 1326.5(2) Å(3), Z = 4, R = 0.0379.
Several group 15 compounds of the type EAr3 (Ar = 2-[(dimethylamino)methyl]phenyl; E = As (4), Sb (5), Bi (6)) have been prepared via salt elimination reactions of 2-(Me2NCH2)C6H4Li and ECl3. Treatment of the lithium salt of the 8-(dimethylamino)-1-naphthyl ligand (Ar‘) with AsCl3 afforded a triaryl derivative, AsAr‘3 (7). The X-ray crystal structures of 4−7 are described, and the observed trends in the degree of intramolecular coordination of the nitrogen atoms are discussed. Crystal data for 4: monoclinic, space group P21/c, a = 8.9336(6) Å, b = 16.347(2) Å, c = 17.875(2) Å, β = 102.540(7)°, V = 2548.2(4) Å3, Z = 4, R = 0.0579. Crystal data for 5: monoclinic, space group P21, a = 9.288(2) Å, b = 18.356(4) Å, c = 15.566(2) Å, β = 90.28(2)°, V = 2654.1(8) Å3, Z = 4, R = 0.0520. Crystal data for 6: monoclinic, space group P21, a = 9.2996(12) Å, b = 18.445(3) Å, c = 15.601(2) Å, β = 90.076(11)°, V = 2676.1(7) Å3, Z = 4, R = 0.0783. Crystal data for 7: monoclinic, space group P21/c, a = 9.5744(12) Å, b = 16.273(2) Å, c = 18.884(3) Å, β = 100.708(11)°, V = 2890.9(7) Å3, Z = 4, R = 0.0495.
The reaction between equimolar quantities of BiCl3 and the silylphosphine P(SiMe3)3 in toluene or THF (tetrahydrofuran) solution affords a black precipitate with the composition of bismuth phosphide, BiP, which has been examined by EDXA, SEM, XPS, powder XRD, solid-state 31P NMR spectroscopy, and elemental analysis. Alternative possible routes to BiP involving the reactions between Na3P and BiCl3 and between Bi(NMe2)3 and P(SiMe3)3 have also been investigated, both of which afford black powders of composition close to BiP, although in the latter case there is some contamination with bismuth metal. Analogous reactions with either SbCl3 or AsCl3 and P(SiMe3)3 afford black and dark brown precipitates, respectively, which are formulated as the materials antimony phosphide, SbP, and arsenic phosphide, AsP, on the basis of similar analyses. Preliminary experiments have also shown that the related arsenides, BiAs and SbAs, can be prepared from reactions between either BiCl3 or SbCl3 and the silylarsine As(SiMe3)3, and that a ternary phase with the composition BiSbP2 is formed in the reaction between BiCl3, SbCl3, and P(SiMe3)3 in a 1:1:2 mole ratio. A material of composition close to elemental phosphorus is obtained from the reaction between PCl3 and P(SiMe3)3.
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