Syntheses and Crystal Structures of Silver(I) Complexes by Depolymerizing [Ag(C≡CPh)]_n with a NP_3

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Two silver(I) complexes were prepared by the reaction of [Ag(C≡CPh)]n with NP3 [NP3 = N(CH2CH2PPh2)3] or with NP3 and [Cu(CH3CN)4]ClO4. Complex 1 [(Ag2Cl(NP3)2)(Ag5- (C≡CPh)6)] contains both NP3 and PhC≡C- ligands. The complex cation is (Ag2Cl(NP3)2)+, in which two Ag(NP3)+ cations were bridged by a Cl- donor. The anion is (Ag5(C≡CPh)6)-, where five Ag+ ions are linked by six C≡CPh- to form a pentanuclear cluster. Complex 2 only contains NP3 ligand, where the silver center adopts a trigonal-bipyramidal geometry. Crystal data for 1: C133H116Ag7Cl3- N2P6, Mr = 2789.54, triclinic, space group P1, a = 13.0780(2), b = 15.3678(2), c = 31.2041(3) ?, α = 91.3928(7), β = 90.9328(8), γ = 96.0244(4)o, V = 6233.8(1) ?3, T = 293(2) K, Z = 2, Dc = 1.486 g/cm3, F(000) = 2796, μ = 1.266 mm-1, the final R = 0.0746 and wR = 0.1953 for 16475 observed reflections with I > 2σ(I). Crystal data for 2: C42H42AgClNO4P3, Mr = 861.00, trigonal, space group R3, a = 17.451(1), b = 17.451(1), c = 11.3985(7) ?, V = 3006.0(3) ?3, T = 293(2) K, Z = 3, Dc = 1.427 g/cm3, F(000) = 1326, μ = 0.731 mm-1, the final R = 0.0251 and wR = 0.0663 for 1499 observed reflections with I > 2σ(I). [Ag (C≡CPh)] n with NP3 [NP3 = N (CH2CH2PPh2) 3] or with NP3 and [Cu (CH3CN) 4] ClO4 Complex 1 [(Ag2Cl (NP3) 2) (Ag5- (C≡CPh) 6)] both both NP3 and PhC≡C-ligands. The complex cation is (Ag2Cl (NP3) 2) The anion is (Ag5 (C≡CPh) 6) -, where five Ag + ions are linked by six C≡CPh- to form a pentanuclear cluster. Complex 2 only contains NP3 ligand, where the silver center adopts a trigonal-bipyramidal geometry. c = 31.2041 (3) ?,? = 91.3928 (2), b = 15.3678 (7) β = 90.9328 (8) γ = 96.0244 (4) o V = 6233.8 (1)? 3 T = 293 (2) K Z = 2 Dc = 1.486 g / cm3 F = 2796, μ = 1.266 mm-1, the final R = 0.0746 and wR = 0.1953 for 16475 observed reflections with I> 2σ (I). Crystal data for 2: C42H42AgClNO4P3, Mr = 861.00, trigonal, space group R3, a = 17.451 (1), b = 17.451 (1 , C = 11.3985 (7) ?, V = 3006.0 (3)? 3, T = 293 (2) K, Z = 3, Dc = 1.427 g / cm3, F (000) = 1326 and μ = 0.731 mm- 1, the final R = 0.0251 and wR = 0.0663 for 1499 observed reflections with I> 2σ (I).
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