Organometallic Compounds of the Lanthanides. 158.1 Alkenyl-Functionalized Cyclopentadienyl Complexes of Yttrium, Samarium, and Lutetium and Their Hydroboration
Organometallic Compounds of the Lanthanides. 158.1 Alkenyl-Functionalized Cyclopentadienyl Complexes of Yttrium, Samarium, and Lutetium and Their Hydroboration
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DOI：
10.1021/om020654b
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发表时间：
2003
期刊：
影响因子：
2.8
通讯作者：
H. Schumann;A. Heim;and Jörg Demtschuk;S. Mühle
中科院分区：
文献类型：
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作者：
H. Schumann;A. Heim;and Jörg Demtschuk;S. Mühle
YCl3、SmCl3 和 LuCl3 与（四甲基乙烯基环戊二烯基）锂 (1a) 反应，生成 (CH2CHC5Me4)2Ln(μ-Cl)2Li(Et2O)2 (Ln = Y (2a)、Sm (2b)、Lu (2c)）。 LuCl3 和类似的钾盐 1b 形成低聚物 [(CH2CHC5Me4)2Lu(μ3-Cl)2K(THF)]n (3)。用 MeLi 将钇配合物 2a 甲基化，得到 (CH2CHC5Me4)2Y(μ-CH3)2Li(THF) (4)。配合物 2a−c 与 9-BBN 的硼氢化反应形成 (C8H14BCH2CH2C5Me4)2Ln(μ-Cl)2Li(THF)2 (Ln = Y (5a), Sm (5b), Lu (5c))。 YCl3 与 2 当量的 K[C5H4CHC6H10] (6) 或 K[C5H4CHCMe2] (10) 反应，得到二聚复合物 [(C6H10CHC5H4)2Y(μ-Cl)]2 (7) 和 [(Me2CCHC5H4)2Y(μ-Cl)]2 (11)，而 SmCl3 与 2 当量的 6 或如图10所示，分别产生三(环戊二烯基)衍生物(C6H10CHC5H4)3Sm(THF)(9)和(Me2CCHC5H4)3Sm(THF)(13)。用 MeLi 甲基化 7 产生不稳定的 [(C6H10CHC5H4)2Y(μ-CH3)]2 (7a)。 SmI2 和 6 反应形成 (C6H10CHC5H4)2Sm(THF)2 (8)。 11 结晶过程中因某些水引起的水解...
YCl3, SmCl3, and LuCl3 react with (tetramethylvinylcyclopentadienyl)lithium (1a), yielding (CH2CHC5Me4)2Ln(μ-Cl)2Li(Et2O)2 (Ln = Y (2a), Sm (2b), Lu (2c)). LuCl3 and the analogous potassium salt 1b form oligomeric [(CH2CHC5Me4)2Lu(μ3-Cl)2K(THF)]n (3). Methylation of the yttrium complex 2a with MeLi gives (CH2CHC5Me4)2Y(μ-CH3)2Li(THF) (4). Hydroboration of the complexes 2a−c with 9-BBN results in the formation of (C8H14BCH2CH2C5Me4)2Ln(μ-Cl)2Li(THF)2 (Ln = Y (5a), Sm (5b), Lu (5c)). The reaction of YCl3 with 2 equiv of K[C5H4CHC6H10] (6) or K[C5H4CHCMe2] (10) affords the dimeric complexes [(C6H10CHC5H4)2Y(μ-Cl)]2 (7) and [(Me2CCHC5H4)2Y(μ-Cl)]2 (11), whereas SmCl3 reacts with 2 equiv of 6 or 10, yielding the tris(cyclopentadienyl) derivatives (C6H10CHC5H4)3Sm(THF) (9) and (Me2CCHC5H4)3Sm(THF) (13), respectively. Methylation of 7 with MeLi yields unstable [(C6H10CHC5H4)2Y(μ-CH3)]2 (7a). SmI2 and 6 react with formation of (C6H10CHC5H4)2Sm(THF)2 (8). Hydrolysis during crystallization of 11 caused by some wate...