Low Temperature Solid-State Reactions of (NH₄)₂[MS₄] (M = W, Mo) with [Cu(CH₃CN)₄](PF₆) and CuBr in the Presence of Bis(diphenylphosphino)methane (dppm):  Crystal Structures of [MS₄Cu₄(dppm)₄](PF₆)₂ (M = W, Mo), [WS₄Cu₃(dppm)₃]X (X = PF₆, Br), [Cu₃(dppm)₃Br₂]Br, [WS₄Cu₂(dppm)₃], and [(n-Bu)₄N][WS₄Cu₃Br₂(dppm)₂]

Abstract

The solid-state reactions of (NH4)2[MS4] (M = W, Mo), [Cu(CH3CN)4](PF6), and bis(diphenylphosphino)methane (dppm) at 110 °C produced pentanuclear clusters [MS4Cu4(dppm)4](PF6)2 (1, M = W; 2, M = Mo), while the analogous solution reaction in CH2Cl2 for M = W yielded a tetranuclear cluster [WS4Cu3(dppm)3](PF6) (3). On the other hand, the (NH4)2[WS4]/CuBr/dppm reaction system resulted in the formation of a tetranuclear cluster [WS4Cu3(dppm)3]Br (4) either in solid at 110 °C or in CH2Cl2, where the solid-state reaction gave also [Cu3(dppm)3Br2]Br (5) as a side product. When the solid-state reactions between (NH4)2[WS4], [Cu(CH3CN)4](PF6) (or CuBr), and dppm were carried out under the presence of [(n-Bu)4N]Br, [WS4Cu2(dppm)3] (6) and [(n-Bu)4N][WS4Cu3Br2(dppm)2] (7) were generated, respectively, while the corresponding solution reactions in CH2Cl2 gave rise to 3 and 4. Compounds 1−7 were fully characterized. 1 crystallizes in the orthorhombic space group Pnma with a = 37.871(6) Å, b = 19.667(4) Å, c = 14.836(4) Å, and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 38.00(3) Å, b = 19.65(1) Å, c = 14.80(1) Å, and Z = 4. 3·CH2Cl2 crystallizes in the monoclinic space group P21 with a = 13.185(5) Å, b = 17.234(6) Å, c = 17.791(2) Å, β = 90.83(4)°, and Z = 2. 4·CH2Cl2 crystallizes in the monoclinic space group P21 with a = 12.94(2) Å, β = 17.06(1) Å, c = 17.875(7) Å, b = 93.7(1)°, and Z = 2. 5·2(CH3)2CHOH crystallizes in the triclinic space group P1̄ with a = 15.613(5) Å, β = 18.440(6) Å, c = 14.191(8) Å, α = 99.86(4)°, β = 104.14(4)°, γ = 86.79(3)°, and Z = 2. 6·CH2Cl2 crystallizes in the triclinic space group P1̄ with a = 14.60(3) Å, b = 25.6(1) Å, c = 10.98(1) Å, α = 92.9(3)°, β = 105.1(1)°, γ = 78.7(4)°, and Z = 2. 7·1.5CH2Cl2 crystallizes in the monoclinic space group P21/n with a = 10.842(3) Å, b = 31.08(2) Å, c = 22.713(5) Å, β = 101.29(2)°, and Z = 4