新型桥联双四面体簇合物的合成与表征

Synthesis and Characterization of Novel Linked Clusters

利用 (μ3-CCO2 Et) Co3(CO) 9与单阴离子试剂 [Mo(CO) 3(η5-C5H4 R) ]- [R=H,C(O) Me]的反应合成了 2个新的含 CCo2 Mo骨架的簇合物 (μ3-CCO2 Et) Co2 Mo(CO) 8(η5-C5H4 R) [R=H (1 ) ;R=C(O) Me(2 ) ],进而用其与双阴离子试剂 {- M(CO) 3[η5-C5H4 C(O) ]}2 -1 ,4-C6 H4 [M=Mo,W]反应合成了 4个双四面体簇合物 {(μ3-CCO2 Et) Co Mo M(CO) 7(η5-C5H4 R) [η5-C5H4 C(O) ]}2 -1 ,4-C6 H4 [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,1 H NMR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 .1 2 64(3 ) nm,b=1 .1 879(3 ) nm,c=3 .3 5 65 (1 0 ) nm,β=93 .3 2 0 (5 )°,V=4.484(2 ) nm3,Z=8,Dc=1 .867g· cm- 3,F(0 0 0 ) =2 480 ,R=0 .0 3 69,w R=0 .1 1 5

The reactions of ( μ 3 CCO 2Et)Co 3(CO) 9 with [Mo(CO) 3( η 5 C 5H 4R)] - [R=H or C(O)Me] gave rise to the formation of ( μ 3 CCO 2Et)Co 2Mo(CO) 8( η 5 C 5H 4R) (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[ η 5 C 5H 4C(O)]} 2 1,4 C 6H 4 yielded four linked clusters {( μ 3 CCO 2Et)CoMoM(CO) 7( η 5 C 5H 4R)[ η 5 C 5H 4C(O)]} 2 1,4 C 6H 4 [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/H analyses, IR and 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 =1.126 4(3) nm, b =1.187 9(3) nm, c =3.356 5(10) nm, β =93.320(5)°, V =4.484(2) nm 3 , Z =8, D c =1.867 g·cm -3 , F(000)=248 0, R=0.036 9, wR = 0.115 0 .