Mo_2S_4[S_2CNC_4H_8]_2的合成、结构表征及其与Cu^+,Ni^(2+)的反应

Synthesis and Structural Characterization of Mo_2S_4[S_2CNC_4H^(?)_8]_2 and Its Reactions with Cu^+, Ni^(2+)

由(NH_4)_2Mo_2S_(12)·2H_2O和(NH_4)(S_2CNC_4H_8)在PPh_3参与反应下,获得Mo_2S_4(S_2CNC_4H_8)_2化合物(1),对此二核钼簇合物进行了红外、电子光谱、电化学及单晶X射线结构表征,并尝试与多种金属化合物进行[2+1]反应,从反应产物的晶体结构分析发现了包括金属夺取端基S^(2-)形成Mo_2O_2S_2(S_2CNC_4H_8)_2化合物(2),Cu^+被氧化并夺取配体(S_2CNC_4H_8)^-形成Cu(S_2CNC_4H_8)_2(3)以及Mo(Ⅴ)还原为Mo(Ⅳ),S^(2-)氧化为(S_2)^(2-)而形成Mo_3(μ_3-S)(μ-S_2)_3[S_2CNC_4H_8]_3·I(4)的三种反应,各化合物的结晶学参数如下: 1,三斜,PI,a=0.9057(2),b=1.7162(7),c=0.6578(1)nm,α=90.49(3)°,β=102.12(2)°,γ=96.57(3)°,V=0.9926(5)nm^3,Z=2,D_0=2.05 g/cm^3,R=0.045,R_w=0.052. 2,三斜,PI,a=0.8754(2),b=1.6560(4),c=0.6678(2)nm,α=97.74(2)°,β=97.90(2)°,γ=80.31(2)°,V=0.9390(4)nm^3,Z=2,D_0=2.05g/cm^3,R=0.036,R_w=0.043. 3,三斜,PI,a=0.748B(2),b=0.8070(2),c=0.6381(1)nm,α=104.86(2)°,β=94.06(2)°,γ=76.59(2)°,V=0.3623(2)nm^3,Z=1,D_0=1.63g/cm^3,R=0.042,R_w=0.051. 4,单斜,P2_1/a,a=1.6488(8),b=1.7043(9),c=1.1349(4)nm,β=90.34(5)°,V=3.189(3)nm^3,Z=4,D_c=2.24g/cm^3,R=0.050,R_w=0.058. 文中对反应及产物的结构特征进行了讨论.

Mo_2S_4[S_2CNC_4H_8]_2 (1) is obtained by the reaction of (NH_4)_2Mo_2S_(12)·2H_2O with (NH_4) [S_2CNC_4H_8] in the presence of PPh_3. The compound 1 has been characterized by IR, UV-Vis, electrochemistry, and X-ray crystallography. Attempts have also been made to carry out [2+1] reactions between 1 and several other metals such as Cu^+ and Ni^(2+). It is found from the structural analysis of the products that there are three kinds of reactions including the capture of terminal S^(2-) by the metal ions to yield Mo_2O_2S_2[S_2CNC_4H_8]_2(2); the oxidation of Cu^+ and the capture of [S_2VNC_4H_8]^- ligands to form Cu[S_2CNC_4H_8]_2(3) and the reduction of Me(Ⅴ) to Mo(Ⅳ) and the oxidation of S^(2-) to (S_2)^(2-) to give {Mo_3S_7[S_2CNC_4H_8]_3·I}(4). The crystal data of each compound are as follows, 1 triclinic, P, a=0.9057(2), b=1.7162(7), c=0.6578(1)nm, α=90.49(3)°, β=102.12(2)°, γ=96.57(3)°, V=0.9926(5)nm^3, Z=2, D_c=2.05g/cm^3, R=0.045, R_w=0.052. 2 triclinic, P, a=0.8754(2), b=1.6560(4), c=0,6678(2)nm, α=97.74(2)°, β=97.90(2)°, γ=80.31(2)°, V=0.9390(4)nm^3, Z=2, D_c=2.05g/cm^3, R=0.036, R_w=0.043. 3 triclinic, P, a=0.7483(2), b=0.8070(2), c=0.6381(1)nm, α=104.86(2)°, β=94.06(2)°, γ=76.59(2)°, V=0.3623 (2)nm^3, Z=1, D_c=1.63g/cm^3, R=0.042, R_w=0.051. 4 Monoclinic, P2_1/a, a=1.6488(8), b=1.7043(9), c=1.1349(4)nm, β=90.34(5)° V=3.189(3)nm^3, Z=4, D_c=2.24g/cm^3, R=0.050, R_w=0.058. Finally, the reactivities of 1 and the structures of these crystals are discussed.