铁钼硫原子簇化合物的合成与结构研究 Ⅴ.[MoFe_3S_4]类立方烷簇合物的转化反应和[Et_4N]_3[Mo_2Fe_6S_8(SC_6H_4CH_(3-m))_3Cl_6]的晶体结构  

Synthesis and Structural Studies of Mo-Fe-S Compounds——V. Transformation of Cluster Skeletons of Compounds with [MoFe_3S_4] Unit and Crystal Structure of [Et_4N]_3[MO_2Fe_6S_8Cl_6(SC_6H_4CH_3-m)_3]

作　　者：康北笙[1] 蔡进华[1] 吴达旭[1] 刘汉钦[1] 刘秋田[1] 翁林红[1] 卢嘉锡[1] 

机构地区：[1]中国科学院福建物质结构研究所

出　　处：《化学学报》1989年第8期744-750,共7页Acta Chimica Sinica

基　　金：福建省自然科学基金;国家自然科学基金;武汉物理所波谱与原子分子物理开放实验室基金

摘　　要：具[MoFe_3S_4]类立方烷结构单元的双类立方烷化合物[Et_4N]_4[Mo_2Fe_7S_8(SR)_(12)](1a,R=Ph;1b,R=tolyl-m)或单类立方烷化合物[MoFe_3S_4(dtcR_2)_5](2a,R=Me;2b,R=Et)与酰氯在乙腈中反应,分别得到不含Fe桥的双类立方烷化合物(Et_4N)_3[Mo_2Fe_6S_8(SR)_3Cl_6](3a,R=Ph;3b,R=tolyl-m)与[MoFe_3S_4]骨架支解后的Fe(dtcR_2)_2Cl(4a,R=Me;4b,R=Et)。说明在相同反应条件下,[MoFe_3S_4]单元在1中比在2中稳定。本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及~1H NMR谱的证实。本文报道3b的单晶结构及3的~1H NMR数据。3b属六方晶系,P6_3/m,a=1.6827(3),c=1.5951(16)nm;V=3.91158nm^3;D_c=1.491g/cm^3;Z=2;F(000)=1780;偏离因子R=0.048。化合物2与酰氯反应产生4,由红外及紫外可见光谱证实。Dicubane cluster compounds [Et_4N]_4 [Mo_2Fe_7S_8 (SR)_(12)] (R=Ph, 1a; R=tolyl-m, 1b) or monocubane cluster compounds [MoFe_3S_4 (dtcR_2)_5] (R=Me, 2a; R=Et, 2b) reacted with MeCOC1 in aeetonitriie to give dieubane compounds [Et_4N]_3 [Mo2F%Ss016 (SR)8] (R -=Ph, aa; R=toiyl-q~, 3b) without bridging Fe atom and Fe(d^eR2)a01 (R--Me, 4a; R -=Et, 4b) without the [MoFe3S~] skeleton respeetively. These reaetons indieate that under similar reaetion conditions, the [MoFesS4] eubane-like unit is more sfable in l than in 2. We also for the first time correlated strueture 1 with structure 3 by ohemieal reae^ions. Single orystal of Sb is hexagonal, spa^e group ~68/~, a-- 1.6827 (3), e = 1.5951 (16)nm; V=3.91158nm3; Z--2; Dc=l.491g/emS; F(000)==1780. With use of 1295 unique data, the structure was refined to R--0.048. We also repor~ ~he spectral daf~ of oompounds 3 and 4.

关 键 词：铁钼硫原子簇化合物 合成 结构 固氮酶 模拟酶 活性中心 

分 类 号：Q554.9[生物学—生物化学] O641.4[理学—物理化学]