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用Co2(CO)8分别与两个杂环配体C(S)NHP(S)(C6H4OCH3)OC(Ph)CH(L1)和C(S)NHC(CH3)2P(S)(Cl)N(Ph)(L2)反应,合成两个新的三核钴羰基硫簇合物Co3(CO)7(μ3-S)犤μ,η2-CNP(S)(C6H4OCH3)OC(Ph)CH犦(Ⅰ)和Co3(CO)7(μ3-S)犤μ,η2-SCNC(CH3)2P(S)(Cl)N(Ph)犦(Ⅱ)。用元素分析,IR,1HNMR,31PNMR及MS谱表征了它们的结构,同时用X射线衍射法测定了它们的晶体分子结构,二者属于三斜晶系,P1珔空间群,Ⅰ的晶胞参数为:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.601(3)°,γ=88.535(2)°,V=1.4318(5)nm3,Z=2,Dc=1.641g·cm-3,F(000)=716,μ=1.893mm-1,R=0.0602,Rw=0.1515。Ⅱ的晶胞参数为:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm3,Z=2,Dc=1.841g·cm-3,F(000)=690,μ=2.419mm-1,R=0.0423,Rw=0.1075。Ⅰ和Ⅱ的分子骨架Co3S为三角锥构型,S作为面桥基配体,所有CO作为端基配体与三个Co原子成键。Ⅰ中含有CoCoCN四元环组件,Ⅱ中含有CoCoSCN五元环组件。
C (S) (Cl) N (C) N (CH3) 2P (S) Two New Trinuclear Cobalt Carbonyl Sulfide Clusters Co3 (CO) 7 (μ3-S) 犤 μ, η2-CNP (S) (C6H4OCH3) OC (Ph) CH 犦Ⅰ) and Co3 (CO) 7 (μ3-S) 犤μ, η2-SCNC (CH3) 2P (S) (Cl) N (Ph) 犦 (Ⅱ). Their structures were characterized by elemental analysis, IR, 1HNMR, 31PNMR and MS spectra. Their crystal molecular structures were also determined by X-ray diffraction. They belong to the triclinic system, P1 珔 space group, unit cell parameters of Ⅰ Is α = 86.926 (1) °, β = 81.601 (3) °, γ = 88.535 (2) ° for a = 0.84768 nm, b = 1.19049 nm, c = 1.43639 nm, V = 1.4318 (5) nm3, Z = 2, Dc = 1.641 g · cm -3, F (000) = 716, μ = 1.893 mm -1, R = 0.0602, Rw = 0.1515. The cell parameters of Ⅱ are as follows: a = 1.2050 (2) nm, b = 1.2448 (2) nm, c = 0.8951 (2) nm, α = 97.49 (1) °, β = 93.552 (3) °, V = 1.2554 (3) nm3, Z = 2, Dc = 1.841 g · cm -3, F (000) = 690, μ = 2.419 mm -1, R = 0.0423, Rw = 0.1075. The molecular frameworks Co3S of Ⅰ and Ⅱ are triangular pyramidal conformations, and S is the ligand of the surface bridge. All COs serve as terminal ligands to bond with three Co atoms. Ⅰ contains CoCoCN four-ring component, Ⅱ contains CoCoSCN five-component ring components.