Huang Kuo-Chih, Tsai Yi-Chou, Lee Gene-Hsiang, Peng Shie-Ming, Shieh Minghuey
Department of Chemistry, National Taiwan Normal University, Taipei 11718, Taiwan, Republic of China, and Instrumentation Center and Department of Chemistry, National Taiwan University, Taipei 10764, Taiwan, Republic of China.
Inorg Chem. 1997 Sep 24;36(20):4421-4425. doi: 10.1021/ic961482b.
The reaction of SeO(2) with Mn(2)(CO)(10)/KOH in methanol solution forms a trigonal bipyramid cluster anion Se(2)Mn(3)(CO)(9) (Ia). Cluster Ia can also be synthesized from the treatment of Se powder with Mn(2)(CO)(10)/KOH in 2:1 molar ratio in methanol solution. If Se is reacted with Mn(2)(CO)(10)/KOH in a molar ratio of 8:1, the deoxygenation occurs to produce a novel cluster Se(8)C(2)Mn(2)(CO)(6)(-) (IIa). Cluster IIa can readily transform into a new octahedral cluster Se(2)Mn(4)(CO)(12)(-) (IIIa) by further treatment with Mn(2)(CO)(10)/KOH in CH(2)Cl(2)/MeOH solutions, and the use of a molar ratio of 1:1 of Se powder to Mn(2)(CO)(10)/KOH in methanol also can yield complex IIIa. In the sulfur-manganese system, the synthesis of the analogous complexes S(2)Mn(3)(CO)(9) (Ib), S(8)C(2)Mn(2)(CO)(6)(-) (IIb), and S(2)Mn(4)(CO)(12)(-) (IIIb) also can be accomplished from the reactions of S powder with Mn(2)(CO)(10)/KOH in similar fashions. Clusters Ia-IIIa and Ib-IIIb are fully characterized by spectroscopic methods or/and X-ray analyses. The novel clusters E(8)C(2)Mn(2)(CO)(6)(-) (E = Se, IIa; E = S, IIb) each consist of two separate Mn(CO)(3) groups which are doubly bridged by two CE(4) fragments. Clusters Ia and Ib each display a trigonal bipyramid framework with two chalcogen atoms in the axial positions, while clusters IIIa and IIIb each exhibit an octahedral metal skeleton.
二氧化硒（SeO₂）与甲醇溶液中的Mn₂(CO)₁₀/KOH反应生成三角双锥簇阴离子[Se₂Mn₃(CO)₉]⁻（Ia）。簇合物Ia也可以通过在甲醇溶液中以2:1的摩尔比用Se粉处理Mn₂(CO)₁₀/KOH来合成。如果Se与Mn₂(CO)₁₀/KOH以8:1的摩尔比反应，则会发生脱氧反应，生成一种新型簇合物[Se₈C₂Mn₂(CO)₆]²⁻（IIa）。通过在CH₂Cl₂/MeOH溶液中用Mn₂(CO)₁₀/KOH进一步处理，簇合物IIa可以很容易地转化为一种新的八面体簇合物[Se₂Mn₄(CO)₁₂]²⁻（IIIa），并且在甲醇中使用Se粉与Mn₂(CO)₁₀/KOH的摩尔比为1:1也可以得到配合物IIIa。在硫 - 锰体系中，类似的配合物[S₂Mn₃(CO)₉]⁻（Ib）、[S₈C₂Mn₂(CO)₆]²⁻（IIb）和[S₂Mn₄(CO)₁₂]²⁻（IIIb）也可以通过S粉与Mn₂(CO)₁₀/KOH以类似方式反应来合成。簇合物Ia - IIIa和Ib - IIIb通过光谱方法或/和X射线分析进行了全面表征。新型簇合物[E₈C₂Mn₂(CO)₆]²⁻（E = Se，IIa；E = S，IIb）各自由两个独立的Mn(CO)₃基团组成，它们由两个CE₄片段双桥连。簇合物Ia和Ib各自呈现出一个三角双锥框架，其中两个硫族原子位于轴向位置，而簇合物IIIa和IIIb各自呈现出一个八面体金属骨架。
