新型桥联双四面体簇合物的合成与表征

利用(μ₃-CCO₂Et)Co₃(CO)₉与单阴离子试剂[Mo(CO)₃(η⁵-C₅H₄R)]-[R=H,C(O)Me]的反应合成了2个新的含CCo₂Mo骨架的簇合物(μ₃-CCO₂Et)Co₂Mo(CO)₈(η⁵-C₅H₄R)[R=H(1);R=C(O)Me(2)],进而用其与双阴离子试剂{-M(CO)₃[η⁵-C₅H₄C(O)]}₂-1,4-C₆H₄[M=Mo,W]反应合成了4个双四面体簇合物{(μ₃-CCO₂Et)CoMoM(CO)₇(η⁵-C₅H₄R)[η⁵-C₅H₄C(O)]}₂-1,4-C₆H₄[M=Mo,R=H(3);M=Mo,R=C(O)Me(4);M=W,R=H(5);M=W,R=C(O)Me(6)].这6个化合物的C和H元素分析,IR,¹HNMR等表征都与其结构一致.晶体X射线衍射分析表明,化合物2属单斜晶系,C₂/c空间群,晶胞参数a=1.1264(3)nm,b=1.1879(3)nm,c=3.3565(10)nm,β=93.320(5)°,V=4.484(2)nm₃,Z=8,D_c=1.867g·cm^-3,F(000)=2480,R=0.0369,wR=0.1150.

Synthesis and Characterization of Novel Linked Clusters

The reactions of (μ₃ CCO₂Et)Co₃(CO)₉ with [Mo(CO)₃ (η⁵ C₅H₄R)] - [R=Hor C(O)Me] gave rise to the formation of (μ₃ CCO₂Et)Co₂Mo(CO)₈ (η⁵ C₅H₄R) (1), C(O)Me(2)]. The further reaction of cluster 1 or 2. The further reaction of cluster 1 or 2 with {(M(CO)₃[ η⁵ C₅H₄C(O)]}₂1, 4 C₆H₄ yielded four linked clusters { (μ₃ CCO₂Et)CoMoM(CO)₇ (η⁵ C₅H₄R)[ η⁵ C₅H₄C(O)]}₂1, 4 C₆H₄ [M=Mo, R=H[STHZ](3); M=Mo, R=C(O)Me(4); M=W, R=H(5); M=W, R=C(O)Me(6)].. All these clusters were characterized by C/Hanalyses, IRand ¹H NMR. The crystal structure of cluster 2 was determined by single crystal X-ray diffraction method. The crystal belongs to monoclinic system with space group, C₂/c and lattice parameters, a=1.1264(3) nm, b=1.1879(3) nm, c=3.3565(10) nm, β =93.320(5)°, V=4.484(2) nm³, Z=8, D_c=1.867 g·cm^-3, F(000)=2480, R=0.0369, wR= 0.1150.