Institute of Inorganic Chemistry, University of Cologne, Greinstraße 6, D-50939 Cologne, Germany.
Inorg Chem. 2013 Apr 1;52(7):4002-10. doi: 10.1021/ic400030j. Epub 2013 Mar 12.
The reaction of Cerium Ammonium Nitrate (CAN) with varying amounts of KO(t)Bu produced homometallic Ce(O(t)Bu)4(NC5H5)2 (1) and the heterometallic derivative KCe2(O(t)Bu)10 (3) characterized by X-ray diffraction and NMR spectroscopy. The oxo-alkoxide cluster Ce3O(O(t)Bu)9 (2) was obtained from a solution of cerium(IV) tetrakis(tert-butoxide) in n-heptane under stringent precautions to avoid any adventitious hydrolysis. Lewis acid-base reactions of in situ generated Ce(O(t)Bu)4(THF)2 (THF = tetrahydrofuran) with bi- and trivalent metal alkoxides [M(O(t)Bu)x]n (M = Ge, Sn; x = 2; n = 2; M = Pb, x = 2; n = 3; M = Al, Fe; x = 3; n = 2) resulted in volatile products of the general formula MCe(O(t)Bu)(4+x) (M = Al (4), Fe (5); x = 3; M = Ge (8), Sn (9), Pb (10); x = 2) in high yields. By dissolving 4 and 5 in pyridine the solvent adducts MCe(O(t)Bu)7(NC5H5) (M = Al (6), Fe (7)) were formed, whereas 8 and 9 reacted with Mo(CO)6 in boiling toluene to yield the termetallic complexes (CO)5MoM(μ2-O(t)Bu)3Ce(O(t)Bu)3 (M = Ge (11), Sn (12)). The new compounds were characterized by comprehensive spectral studies, mass spectroscopy, and single crystal X-ray diffraction analysis.
硝酸铈铵（CAN）与不同量的 KO(t)Bu 反应生成同核铈（O(t)Bu）4(NC5H5)2（1）和异核衍生物 KCe2(O(t)Bu)10（3），通过 X 射线衍射和 NMR 光谱进行了表征。在严格的预防措施下，从铈（IV）四（叔丁醇）在正庚烷中的溶液中获得了氧-醇盐簇 Ce3O(O(t)Bu)9（2），以避免任何偶然的水解。原位生成的 Ce(O(t)Bu)4(THF)2（THF = 四氢呋喃）与二价和三价金属醇盐[M(O(t)Bu)x]n（M = Ge，Sn；x = 2；n = 2；M = Pb，x = 2；n = 3；M = Al，Fe；x = 3；n = 2）的路易斯酸碱反应产生了挥发性产物，其通式为 MCe(O(t)Bu)(4+x)（M = Al（4），Fe（5）；x = 3；M = Ge（8），Sn（9），Pb（10）；x = 2），产率高。通过将 4 和 5 溶解在吡啶中，形成了溶剂加合物 MCe(O(t)Bu)7(NC5H5)（M = Al（6），Fe（7）），而 8 和 9 与 Mo(CO)6 在沸腾的甲苯中反应生成了双核配合物（CO）5MoM(μ2-O(t)Bu)3Ce(O(t)Bu)3（M = Ge（11），Sn（12））。这些新化合物通过综合光谱研究、质谱和单晶 X 射线衍射分析进行了表征。
