羰基过渡金属异核原子簇(PPh_3)_2CuFe_2Co(CO)_8(μ_3-S)和(PPh_3)_3AuFe_2Co(CO)_7(μ_3-S)的合成与表征

SYNTHESIS AND CHARACTERIZATION OF TRANSITION METAL CARBONYL HETEROG CLEAR CLUSTERS (PPh_3)_2CuFe_2Co(OQ)_8(μ_3-S) and (PPh_3)_3AuFe_2Co(CO)_7(μ_3-S)

本文利用高压法制备HFe_2Co(CO)_9(μ_3-S),作为原料,经脱质子化作用,再分别与(PPh_3)_2Cu(NO_3)和PPh_3AuCl反应,将Ph_3Cu-或Ph_3Au-联接到原始簇合物的中心骨架上,使簇核扩大,得到了组成为(PPh_3)_2CuFe_2Co(CO)_(?)(μ_3-S)和(PPh_3)_3AuFe_2Co(CO)_(?)(μ_3-S)的化合物.文中对此两个新化合物进行了IR,UV,~1H和^(31)P NMR.元素分析、熔点测定等性质表征,并对(PPh_3)_2CuFe_2Co(CO)_(?)(μ_3-S)进行了单晶X-射线衍射分析.两个化合物具有类似的中心骨架,在Fe_2和Co原子三角形的上面和下面分别键联着Cu和S,或Au和S原子,构成了三角双锥结构.其中一个簇合物由二个三苯基膦和八个羰基配位,另一个则由三个三苯基膦和七个羰基配位.

HFe2Co(CO)8(μ3-S) as a starting material was synthesized with a high-pressure method, it was deprotonated in the presence of base and the resultant anion reacted with (PPh3)2CuNO or PPh3AuCl to produce (PPh3)2CuFe2Co(CO),(μ3-S) and (PPh3)3AuFe2Co(CO)7(μ3-S) respectively in which (PPh3)Cu- or PPh3Au- is bonded to a centric core of the starting cluster to form a larger cluster. In this paper, these two compounds were characterized by IR, UV, 1H NMR, 31P NMR, the elementary analysis and melting point were determined and the single crystal structure was carried out by XRD for (PPh3)2CuFe2Co(CQ)8(μ3-S). Both clusters have a similar core structure, Cu (or Au) and S atoms bonded upon and under the Fe2-Co atoms triangle plane rcspectivelt form a trigonal bipyramidal structure. One cluster is coordinated by two triphenylphosphine molecules and eight carbonyls and the other by three triphcnylphosphine molecules and seven carbony's.