SYNTHESIS AND PROTON MAGNETIC-RESONANCE PROPERTIES OF FE3MS4 (M=MO OR W) CUBANE-LIKE CLUSTER DIMERS
SYNTHESIS AND PROTON MAGNETIC-RESONANCE PROPERTIES OF FE3MS4 (M=MO OR W) CUBANE-LIKE CLUSTER DIMERS
复制标题
DOI：
10.1039/dt9800002354
复制
发表时间：
1980-01-01
期刊：
影响因子：
--
通讯作者：
GARNER, CD
中科院分区：
文献类型：
--
作者：
CHRISTOU, G;GARNER, CD
详细介绍了[Fe_6 M_2S_8（SR）_9]_（3-）（其中M = Mo，R = Ph，C_6 H_4Cl_p，C_6 H_4 Me_p，Et;或M = W，R = Et）和[Fe_6 M_2S_8（SPh）_6（OMe）_3]_（3-）（其中M = Mo或W）的合成方法。300 MHz 1H n.m.r.这些配合物和[Fe_6Mo_2S_8Cl_6（SR′）_3]_3-（其中R′= Et或Ph）在[2H_6]二甲基亚砜中的光谱已被记录。20和80 °C。对于所有的配合物，桥接和终端配体之间的明显区别观察到，在每组桥接和终端配体，只有一个共振观察到每个化学上不同的质子。桥连配体表现出小得多的各向同性位移比那些相应的配体在终端的位置和所有的位移的幅度随着温度的升高而降低。末端配体的各向同性位移似乎主要是通过π-（芳基硫醇基）或σ-（烷基硫醇基）自旋离域机制的接触;然而，对于桥接区域，接触和偶极机制似乎都是有效的，后者对µ2-甲氧基桥接络合物特别重要。
Synthetic procedures leading to the preparation of the complexes [Fe6M2S8(SR)9]3–(where M = Mo and R = Ph, C6H4Cl-p, C6H4Me-p, or Et; or M = W and R = Et) and [Fe6M2S8(SPh)6(OMe)3]3–(where M = Mo or W) are detailed. 300 MHz 1H n.m.r. spectra have been recorded for these complexes and [Fe6Mo2S8Cl6(SR′)3]3–(where R′= Et or Ph) in [2H6]dimethyl sulphoxide at temperatures between ca. 20 and 80 °C. For all complexes, a clear distinction between bridging and terminal ligands is observed and, within each set of bridging and terminal ligands, only one resonance is observed for each chemically different proton. The bridging ligands exhibit much smaller isotropic shifts than those for the corresponding ligands in the terminal positions and all of the shifts decrease in magnitude with an increase in temperature. The isotropic shifts of the terminal ligands appear to be predominantly contact in origin via a π-(arylthiolato-groups) or σ-(alkylthiolato-groups) spin delocalisation mechanism; however, for the bridging region both contact and dipolar mechanisms seem to be operative, the latter being of particular importance for the µ2-methoxo-bridged complexes.