SYNTHETIC ROUTES TO FE2S2, FE3S4, FE4S4, AND FE6S9 CLUSTERS FROM THE COMMON PRECURSOR [FE(SC2H5)4]2- - STRUCTURES AND PROPERTIES OF [FE3S4(SR)4]3- AND [FE6S9(SC2H5)2]4-, EXAMPLES OF THE NEWEST TYPES OF FE-S-SR CLUSTERS
SYNTHETIC ROUTES TO FE2S2, FE3S4, FE4S4, AND FE6S9 CLUSTERS FROM THE COMMON PRECURSOR [FE(SC2H5)4]2- - STRUCTURES AND PROPERTIES OF [FE3S4(SR)4]3- AND [FE6S9(SC2H5)2]4-, EXAMPLES OF THE NEWEST TYPES OF FE-S-SR CLUSTERS
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DOI：
10.1021/ja00350a028
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发表时间：
1983-01-01
影响因子：
15
通讯作者：
HOLM, RH
中科院分区：
文献类型：
--
作者：
HAGEN, KS;WATSON, AD;HOLM, RH
强还原性四面体Fe（II）配合物[Fe（SEt）4] 2”（1）作为Fe-S-SR簇合物的通用前体。1与1.0-1.5当量的单质硫反应，生成[Fe_2S_2（SEt）_4]_（2）、[Fe_3S_4（SEt）_4]_（3）和[Fe_6S_9（SEt）_2]_（4）三种簇合物。在乙腈中，在~ 25 ℃下，1和1.0当量硫以80%产率提供2的（Me 3 NCH 2 Ph）+盐.该化合物在乙腈中于80 ℃定量转化为先前已知的[Fe 4S 4（SEt）4] 2~（5）。在丙酮中，25 ℃，1.4当量硫，生成[Fe_3S_4（SEt）_4]_3 ~（66%）的Et_4N ~+盐。在60 ℃下，在乙腈中（Et 4 N）3（3）转化为（Et 4 N）4（4）（32%），其也可以在85 ℃下由1和1.5当量的硫在乙腈中以更高的产率获得.集群2和集群5是已经建立的结构类型的示例。（Et 4 N）3 [Fe 3S 4（SPh）4]，由3通过用苯乙撑的配体取代而获得，在正交晶系空间群Pna 2l中结晶，其中a= 36.748（4）B= 9.114（2），c= 17.427（4），并且Z= 4。利用7657个唯一数据（I> 3（I）），结构被细化至R= 3.9%。的Fe 3S 8部分的阴离子接近对称性，并由两个四面体的FeS 4单元角连接的中心Fe原子，也在四面体网站。两个外层的Fe原子分别由两个硫醇盐末端配位。[β 3（Sr 2 -8）4]+核心单元是Fe-S团簇结构化学中的一个新的元素，其平均Fe-Fe间距为2.714 μ m，其它尺寸与[Fe 2S 2（SR）4] 2~中的[Fe 2S 2] 2+核心相似。（Et 4 N）4（4）-4MeCN在三斜晶系空间群Pi中结晶，其中a= 11.537（3）π，B=
The strongly reducing, tetrahedral Fe (II) complex [Fe (SEt) 4] 2"(1) serves as a versatile precursor to Fe-S-SR clusters. With 1.0-1.5 equiv of elemental sulfur 1 reacts to form threetypes of clusters,[Fe2S2 (SEt) 4] 2"(2),[Fe3S4 (SEt) 4] 3"(3), and [Fe6S9 (SEt) 2] 4"(4). In acetonitrile at~ 25 C 1 and 1.0 equiv of sulfur afford the (Me3NCH2Ph)+ salt of 2 in 80% yield. This compound is converted quantitatively to previously known [Fe4S4 (SEt) 4] 2~(5) in acetonitrile at 80 C. In acetone at~ 25 C 1 and 1.4 equiv of sulfur give [Fe3S4 (SEt) 4] 3~(66%) as its Et4N+ salt. At 60 C in acetonitrile (Et4N) 3 (3) is converted to (Et4N) 4 (4)(32%), which can also be obtained in higher yield from 1 and 1.5 equiv of sulfur in acetonitrile at 85 C. Clusters 2 and 5 are examples of structural types already established.(Et4N) 3 [Fe3S4 (SPh) 4], obtained from 3 by ligand substitution with benzenethiol, crystallizes in orthorhombic space group Pna2l with a= 36.748 (4) Á, b= 9.114 (2) Á, c= 17.427 (4) Á, and Z= 4. With 7657 unique data (I> 3 (/)) the structure was refined to R= 3.9%. The Fe3S8 portion of the anion approaches symmetry and consists of two tetrahedral FeS4 units corner-linked by a central Fe atom, also in a tetrahedral site. The two outer Fe atoms are each terminally coordinatedby two thiolates. The [ß3 (ĩ2-8) 4]+ core unit, a new element in the structural chemistry of Fe-S clusters, has a mean Fe—Fe separation of 2.714 Á and other dimensions similar to the [Fe2S2] 2+ cores of [Fe2S2 (SR) 4] 2~.(Et4N) 4 (4)-4MeCN crystallizes in triclinic space group Pi with a= 1 1.537 (3) Á, b=