Femoni Cristina, Iapalucci Maria Carmela, Longoni Giuliano, Tiozzo Cristina, Zacchini Stefano, Heaton Brian T, Iggo Jonathan A
Dipartimento di Chimica Fisica ed Inorganica, Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy.
Dalton Trans. 2007 Sep 21(35):3914-23. doi: 10.1039/b708469b. Epub 2007 Jul 30.
The reaction of [Rh7(CO)16]3- with SnCl(2).2H2O in a 1 : 1 molar ratio under N2 results in the formation of the new heterometallic cluster, [Rh12Sn(CO)27]4-, in very high yield (ca. 86%). Further controlled additions of SnCl(2).2H2O, or solutions of HCl, or [RhCl(COD)]2, give [Rh12(mu-Cl)2Sn(CO)23]4-. Similarly, addition of HBr to [Rh12Sn(CO)27]4- gives the related cluster [Rh12(mu-Br)2Sn(CO)23]4-. Notably, if the addition of SnCl(2).2H2O to [Rh12Sn(CO)27]4- is carried out under a CO atmosphere, the reaction takes a different course and leads to the formation of the new cluster, [Rh12Sn(mu3-RhCl)(CO)27]4-. All the above clusters have been shown by single-crystal X-ray diffraction studies to have a metal framework based on an icosahedron, which is centred by the unique Sn atom. Their chemical reactivity and 13C-{103Rh} HMQC NMR spectroscopic characterization are also reported.
在氮气氛围下，[Rh₇(CO)₁₆]³⁻与二水合氯化亚锡按1 : 1摩尔比反应，以非常高的产率（约86%）生成新的异金属簇合物[Rh₁₂Sn(CO)₂₇]⁴⁻。进一步控制添加二水合氯化亚锡、盐酸溶液或[RhCl(COD)]₂，可得到[Rh₁₂(μ-Cl)₂Sn(CO)₂₃]⁴⁻。类似地，向[Rh₁₂Sn(CO)₂₇]⁴⁻中添加HBr可得到相关簇合物[Rh₁₂(μ-Br)₂Sn(CO)₂₃]⁴⁻。值得注意的是，如果在CO气氛下向[Rh₁₂Sn(CO)₂₇]⁴⁻中添加二水合氯化亚锡，反应会采取不同的路径，生成新的簇合物[Rh₁₂Sn(μ₃-RhCl)(CO)₂₇]⁴⁻。单晶X射线衍射研究表明，上述所有簇合物都具有以独特的Sn原子为中心的基于二十面体的金属骨架。还报道了它们的化学反应性和¹³C-{¹⁰³Rh} HMQC NMR光谱表征。
