四核钴羰基簇合物的合成和晶体结构

Synthesis and Crystal Structure of Tetranuclear Cobalt Carbonyl Clusters

用 Co2 (CO) 8与有机杂环二硫代次膦酸盐 SP(C6 H4 OR) (S) N(C6 H5) NC(Me) (R=Me,Et)反应 ,得到两类 4个含 S,P桥基配体的四核钴羰基簇合物 Co4 (CO) 1 0 (μ4 -S) [μ4 -P(C6 H4 OR) ](1 :R=Me;3 :R=Et)和 Co4 (CO) 1 0 (μ3-S) [μ2 -P(C6 H4 OR) N(C6 H5) NC(Me) ](2 :R=Me,4:R=Et) .在反应中 ,前配体中的P S键以及 C— S,P—S,P— N键劈开 ,产生的分子片与金属钴原子配位 ,组建成新的羰基钴簇 .对这 4个簇合物进行了元素分析 ,IR,1 H NMR和 MS谱学表征 ,并测定了簇合物 4的晶体结构 ,该晶体属单斜晶系 ,P2 1 /c空间群 ,晶胞参数 a=1 .90 65 (4 ) nm,b=1 .0 0 81 (2 ) nm,c=1 .6663 (3 ) nm,β=97.3 6(3 )°,V=3 .1 70 4(1 1 ) nm3,Z=4,Dc=1 .743 g/cm3.Co1 Co3 Co4呈三角形分布 ,其中 Co— Co平均键长为 0 .2 5 1 nm,而 Co2在该三角平面的一侧 ,Co2—Co3键为 0 .2 69nm.该簇合物分子骨架为三角钉型结构 ,每个 Co原子的立体几何均为变形八面体 。

The reactions of Co 2(CO) 8 with organic cyclic dithiophosphinate SP(S)(C 6H 4OR)N(C 6H 5)NC(Me)(R=Me, Et) gave four tetranuclear cobalt carbonyl clusters containing capping S, P bridging ligand in Co 4(CO) 10 ( μ 4 S)( μ 4 PC 6H 4OR)(1: R=Me, 3: R=Et) and P⌒C bridging and face bridging S ligand in Co 4(CO) 10 ( μ 3 S)[ μ 2 P(C 6H 4OR)N(Ph)NCMe](2: R=Me, 4: R=Et). During the reactions, the two ligand precursors have cleaved in its PS and/or C-S, P-S, P-N bonds respectively to give the fragments as the ligand as listed above that coordinated to Co atoms to form the new cluster molecules. These clusters have characterized by elementary analysis, IR, 1H NMR and MS spectroscopy. The crystal structure of cluster 4 has been determined by X ray diffraction techniques. The crystal belongs to monoclinic with space group P2 1/c . The cell parameters are as follows: a =1.906 5(4) nm, b =1.008 1(2) nm, c =1.666 3(3) nm, β=97.36(3)° , V =3.170 4(11) nm 3, D c=1.743 g/cm 3, Z =4. The Co-Co average bond length is 0.251 nm in the triangular plane of Co1Co3Co4, the Co2 is linked on the plane to form a spike. The tetracobalt framework is 'spiked triangular'. The stereogeometry of each Co assumes a distorted octahedron with different coordination environments.