[MoFe3S4]3+ and [MoFe3S4]2+ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety
[MoFe3S4]3+ and [MoFe3S4]2+ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety
复制标题
DOI：
10.1016/j.jorganchem.2006.07.047
复制
发表时间：
2007-01-01
影响因子：
2.3
通讯作者：
Tatsumi, Kazuyuki
中科院分区：
文献类型：
--
作者：
Komuro, Takashi;Kawaguchi, Hiroyuki;Tatsumi, Kazuyuki
合成了一系列通式为[Cp* MoFe_3S_4Ln]（m）（Cp* =eta（5）-C_5 Me_5; L = S ′ Bu，SPh，Cl，I，n = 3，m = 1-; L-n = I-2（P ′ Bu-3），m = 0; L = 2，6-二异丙基苯异氰（ArNC），n = 7，m = 1+）的金属钼/铁/硫簇合物。从Cp*Mo（S 'Bu）（3）（1）、FeCl_3、LiS'Bu和S-8的自组装反应中分离出立方烷簇合物（PPh_4）[Cp* MoFe_3S_4（S 'Bu）（3）]（2），而从Cp* MoCl_4/FeCl_3/LiSPh/FeCl_3体系中得到了类似的簇合物（PPh_4）[Cp* MoFe_3S_4（SPh）（3）]（3）。PPh 4 Br反应体系或来自2与PhSH的配体取代反应。2与苯甲酰氯反应生成（PPh 4）[Cp* MoFe 3S 4Cl 3]（4），再与NaI反应生成（PPh 4）[Cp* MoFe 3S 4 I3]（5）。在用P 'Bu-3处理5时生成中性立方烷簇Cp* MoFe 3S 4 I2（P' Bu-3）（6）。虽然4在ArNC存在下被二茂钴还原导致立方烷核的反硝化得到Fe 4S 4（ArNC）（9）Cl（7），但5的类似还原反应产生[Cp* MoFe 3S 4（ArNC）（7）]I（8），其中MoFe 3S 4核保留。通过X射线衍射分析确定了化合物4-6和8的晶体结构。(c)2006 Elsevier B. V.保留所有权利。
A series of organometallic molybdenum/iron/sulfur clusters of the general formula [Cp*MoFe3S4Ln](m) (Cp* =eta(5)-C5Me5; L = S'Bu, SPh, Cl, I, n = 3, m = 1-; L-n = I-2(P'Bu-3), m = 0; L = 2,6-diisopropylphenylisocyanide (ArNC), n = 7, m = 1+) have been synthesized. A cubane cluster (PPh4)[Cp*MoFe3S4(S'Bu)(3)] (2) was isolated from a self-assembly reaction of Cp*Mo(S'BU)(3) (1), FeCl3, LiS'Bu, and S-8 followed by cation exchange with PPh4Br in CH3CN, while an analogous cluster (PPh4)[Cp*MoFe3S4(SPh)(3)](3) was obtained from the Cp*MoCl4/FeCl3/LiSPh/PPh4Br reaction system or from a ligand substitution reaction of 2 with PhSH. Treatment of 2 with benzoyl chloride gave rise to (PPh4)[Cp*MoFe3S4Cl3] (4), which was in turn converted to (PPh4)[Cp*MoFe3S4I3] (5) by the reaction with NaI. A neutral cubane cluster Cp*MoFe3S4I2(P'Bu-3) (6) was generated upon treating 5 with P'Bu-3. Although reduction of 4 by cobaltocene under the presence of ArNC resulted in a disproportionation of the cubane core to give Fe4S4(ArNC)(9)Cl (7), a similar reduction reaction of 5 produced [Cp*MoFe3S4(ArNC)(7)]I (8), where the MoFe3S4 core was retained. The crystal structures of 4-6, and 8 were determined by the X-ray analysis. (c) 2006 Elsevier B.V. All rights reserved.