112421-71-3Relevant academic research and scientific papers
New hydrogen-containing zirconium clusters with phosphine ligands
Chen, Linfeng,Cotton, F. Albert
, p. 105 - 120 (1997)
Reaction of ZrCl4 with 2 equiv. of HSnBu3 followed by addition of phosphines yields hexazirconium cluster compounds [Zr6Cl14H4(PR3)4] (2a: PR3 = PMc2Ph; 2b: PR3 = PEt2Ph; 2c: PR3 = PEt3) and pentazirconium cluster compounds [Zr5Cl12H4(PR3)5] (3a: PR3 = PMe2Ph; 3c: PR3 = PEt3). Treatment of compound 2a with Na/Hg in the presence of PMe2Ph results in the formation of [Zr6Cl12H2(PMe2Ph)6] (4a). When the phosphine ligand is PEt3, a similar reaction leads to the isolation of two new cluster compounds, [Zr6Cl12H3(PEt3)6] [ZrCl5(PEt3)] (5c) and [Zr6Cl13H3(PEt3)5] (6c). In MeCN solution, compound 2a decomposes to form an ionic cluster compound, [HPMe2Ph]4[Zr6Cl18H4] (7a). Cluster hydrogen atoms were observed by 1H NMR spectroscopy for all cluster compounds and by X-ray diffraction study for compound 3c where two hydrogen atoms are μ3-bridging and the other two edge-bridging. In compound 7a, there is evidence for the four hydrogen atoms distributed near the centers of the eight triangular faces of the Zr6 octahedron. When ZrCl4 reacts with 1 equiv. of HSnBu3 followed by addition of PR2Ph, only dinuclear compounds [Zr2Cl4(μ-Cl)2(PR2Ph) 4] (8a: R = Me; 8b: R = Et) are isolated. All compounds were characterized by X-ray crystallography and 1H NMR spectroscopy. Compound 2a · 0.75CH2Cl2 crystallized in the monoclinic space group C2/c with cell dimensions (-100°C) of a = 31.434(9), 6=15.255(6), c= 14.582(8) A, β=106.08(2)°, V=6719(9) A3 and Z=4. Compound 2b-2CH2Cl2 crystallized in the monoclinic space group P21/c with cell dimensions (-60°C) of a= 11.310(1), b= 17.412(5), c= 17.807(2) A, β = 91.55(1)°, V=3505(1) A3 and Z = 2. Compound 2c · 2C6H6 crystallized in the monoclinic space group P21/n with cell dimensions (-150°C) of a= 15.322(6), b= 12.186(3), c= 16.696(7) A, β = 91.09(2)°, V = 3117(2) A3 and Z = 2. Compound 2c crystallized in the monoclinic space group C2/c with cell dimensions (-150°C) of a = 26.128(9), b = 16.826(1), c= 13.411 (4) A, β = 117.07(1)°, V = 5250(2) A3 and Z=4. Compound 3c · C6H5CH3 crystallized in the monoclinic space group C2/c with cell dimensions (-75°C) of a = 48.06(1), b = 12.667(3), c = 22.829(5) A, β = 113.36(2)°, V= 12758(5) A3 and Z = 8. Compound 4a crystallized in the triclinic space groupa P1 with cell dimensions (-60°C) of a = 12.918(3), b= 15.493(2), c = 18.90(1) A, α = 90.31(6), β = 104.37(2), y= 109.89(3)°, V = 3429(2) A3 and Z = 2. Compound 5c · 0.5C6H6 crystallized in the monoclinic space group P2/c with cell dimensions (-60°C) of a = 23.707(6), b = 14.521(2), c = 25.109(3) A β = 92.08(1)°, V=8633(3) A3 and Z = 4. Compound 6c · C6H6 crystallized in the orthorhombic space group Pna21 with cell dimensions (-100°C) of a = 23.496(9), b = 23.973(2), c= 11.638(1) A, V = 6555(3) A3 and Z = 4. Compound 7a · 2MeCN crystallized in the triclinic space group P1 with cell dimensions (20°C) of a = 12.881(2), b = 22.859(3), c =12.208(2) A, α = 98.66(1), γ = 109.99(1), 7=81.39(1)°, V =3320.8(9) A3 and Z = 2. Compound 8b-0.67C6H5CH3 crystallized in the rhombohedral space group R3m with cell dimensions (-100°C) of a = 20.947(3), b = 20.947(3), c = 30.87(1) A, V = 11730(4) A3 and Z = 6.
Synthesis and structural characterization of three compounds with Zr(III)-Zr(III) bonds: Zr2Cl6(dppe)2·2C2H 4Cl2·1.5C6H5CH3, Zr2Cl6(PMe2Ph)4, and Zr2Cl6(PEt3)4
Albert Cotton,Diebold, Michael P.,Kibala, Piotr A.
, p. 799 - 804 (2008/10/08)
The syntheses and crystal and molecular structures of Zr2Cl6(dppe)2·2C2H 4Cl2·1.5C6H5CH3 (1), Zr2Cl6(PMe2Ph)4 (2), and Zr2Cl6(PEt3)4 (3) are described. They were obtained by reduction of ZrCl4 with 1 equiv of sodium amalgam in the presence of the appropriate phosphine. Zr2Cl6(dppe)2·2C2H 4Cl2·1.5C6H5CH3 (1) crystallizes from toluene/dichloroethane in the triclinic space group P1 with unit cell dimensions a = 15.905 (1) A?, b = 20.398 (2) A?, c = 11.859 (2) A?, α = 98.21 (1)°, β = 110.59 (1)°, γ = 97.33 (1)°, V = 3497 (2) A?3, and dcalcd = 1.445 g/cm3 for Z = 2. The structure was refined to R = 0.060 and Rw = 0.069 for 3978 reflections with I > 3σ(I). Zr2Cl6(PMe2Ph)4 (2) crystallizes from toluene in the triclinic space group P1 with unit cell dimensions a = 10.982 (5) A?, b = 11.079 (4) A?, c = 9.838 (4) A?, α = 114.12 (3)°, β = 108.33 (4)°, γ = 86.41 (4)°, V = 1034 (2) A?3, and dcalcd = 1.522 g/cm3 for Z = 1. The structure was refined to R = 0.049 and Rw = 0.072 for 1880 reflections having I > 3σ(I). Zr2Cl6(PEt3)4 (3) crystallizes from toluene in the monoclinic space group P21/n with unit cell dimensions a = 10.570 (2) A?, b = 14.997 (3) A?, c = 13.227 (2) A?, β = 108.54 (2)°, V = 1987 (1) A?3, and dcalcd = 1.450 g/cm3 for Z = 2. The structure was refined to R = 0.047 and Rw = 0.070 for 1815 reflections having I > 3σ(I). All compounds are of the edge-sharing bioctahedron type, having cis phosphine ligands in the same plane as the bridging chlorides, with Zr-Zr distances of 3.104 [5], 3.127 (1), and 3.169 (1) A? for 1, 2, and 3, respectively.
