四核钴羰基簇合物的合成和晶体结构

用Co₂(CO)₈与有机杂环二硫代次膦酸盐SP(C₆H₄OR)(S)N(C₆H₅)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)₁₀(μ₄-S)μ₄-P(C₆H₄OR)](1:R=Me;3:R=Et)和Co₄(CO)₁₀(μ₃-S)μ₂-P(C₆H₄OR)N(C₆H₅)NC(Me)](2:R=Me,4:R=Et).在反应中,前配体中的PS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,¹HNMR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,P2₁/c空间群,晶胞参数a=1.9065(4)nm,b=1.0081(2)nm,c=1.6663(3)nm,β=97.36(3)°,V=3.1704(11)nm₃,Z=4,D_c=1.743g/cm³.Co1Co3Co4呈三角形分布,其中Co-Co平均键长为0.251nm,而Co₂在该三角平面的一侧,Co2-Co3键为0.269nm.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,但配位环境各不相同.

Synthesis and Crystal Structure of Tetranuclear Cobalt Carbonyl Clusters

The reactions of Co₂(CO)₈ with organic cyclic dithiophosphinate SP(S)(C₆H₄OR)N(C₆H₅)NC(Me)(R=Me, Et) gave four tetranuclear cobalt carbonyl clusters containing capping S, Pbridging ligand in Co 4(CO)₁₀ (μ₄-S) (μ₄-PC₆H₄OR)(1: R=Me, 3: R=Et) and P⌒Cbridging and face bridging Sligand in Co₄ (CO)₁₀ (μ₃-S)μ₂-P(C₆H₄OR)N(Ph)NCMe](2:R=Me, 4:R=Et). During the reactions, the two ligand precursors have cleaved in its PSand/or C-S, P-S, P-Nbonds 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 NMRand MSspectroscopy. The crystal structure of cluster 4 has been determined by X-ray diffraction techniques. The crystal belongs to monoclinic with space group P2₁/c. The cell parameters are as follows: a=1.9065(4) nm, b=1.0081(2) nm, c=1.6663(3) nm, β=97.36(3)°, V=3.1704(11) nm³, D_c=1.743 g/cm³, 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.