Heterobi- and Trimetallic Cerium(IV) tert-Butoxides with Mono-, Di-, and Trivalent Metals (M = K(I), Ge(II), Sn(II), Pb(II), Al(III), Fe(III))

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• 作者：Johannes Schl盲fer ; Stefan Stucky ; Wieland Tyrra ; Sanjay Mathur
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：April 1, 2013
• 年：2013
• 卷：52
• 期：7
• 页码：4002-4010
• 全文大小：444K
• 年卷期：v.52,no.7(April 1, 2013)
• ISSN：1520-510X

文摘

The reaction of Cerium Ammonium Nitrate (CAN) with varying amounts of KO^tBu produced homometallic Ce(O^tBu)₄(NC₅H₅)₂ (1) and the heterometallic derivative KCe₂(O^tBu)₁₀ (3) characterized by X-ray diffraction and NMR spectroscopy. The oxo-alkoxide cluster Ce₃O(O^tBu)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^tBu)₄(THF)₂ (THF = tetrahydrofuran) with bi- and trivalent metal alkoxides [M(O^tBu)_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^tBu)_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^tBu)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(渭₂-O^tBu)₃Ce(O^tBu)₃ (M = Ge (11), Sn (12)). The new compounds were characterized by comprehensive spectral studies, mass spectroscopy, and single crystal X-ray diffraction analysis.