Synthesis, Structures, and Properties of “Encapsulated” Iron and Cobalt Metallocenes with Highly Isopropylated Cyclopentadienyl Rings
Synthesis, Structures, and Properties of “Encapsulated” Iron and Cobalt Metallocenes with Highly Isopropylated Cyclopentadienyl Rings
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具有高度异丙基化环戊二烯基环的“封装”铁和钴茂金属的合成、结构和性能
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发表时间：
1997
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通讯作者：
T. Hanusa
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作者：
D. Burkey;M. L. Hays;and Randall E. Duderstadt;T. Hanusa
在四氢呋喃中，K[(i-Pr)3C5H2]和K[(i-Pr)4C5H]分别与CoCl2反应生成双(三异丙基环戊二烯)钴[(i-Pr)3C5H2]2Co和双(四丙基环戊二烯基)钴[(i-Pr)4C5H]2Co。与[(i-Pr)3C5H2]2Co不同的是，[(i-Pr)4C5H]2Co的固体样品在空气中无限稳定。二(三异丙基环戊二烯)铁[(i-Pr)3C5H2]2Fe和双(四丙基环戊二烯)铁[(i-Pr)4C5H]2Fe可以用NOBF4高产率地氧化得到相应的二茂铁盐{[(i-Pr)3C5H2]2Fe}BF4和{[(i-Pr)4C5H]2Fe}BF4。用NH4X(X=[PF6]-，[BPh4]-)氧化[(i-Pr)3C5H2]2Co和[(i-Pr)4C5H]2Co生成钴配合物{[(i-Pr)3C5H2]2Co}X和{[(i-Pr)4C5H]2Co}X，[(i-Pr)4C5H]2m(M=Fe或Co)的氧化速度明显慢于[(i-Pr)3C5H2]2m。报道了中性[(i-Pr)3C5H2]2M金属茂和阳离子{[(i-Pr)3C5H2]2M}+和{[(i-Pr)4C5H]2M}+金属茂的单晶X射线结构。..。
Bis(triisopropylcyclopentadienyl)cobalt, [(i-Pr)3C5H2]2Co, and bis(tetraisopropylcyclopentadienyl)cobalt, [(i-Pr)4C5H]2Co, can be prepared from the reaction of K[(i-Pr)3C5H2] and K[(i-Pr)4C5H], respectively, with CoCl2 in THF. In contrast to [(i-Pr)3C5H2]2Co, solid samples of the “encapsulated” [(i-Pr)4C5H]2Co are indefinitely stable in air. Bis(triisopropylcyclopentadienyl)iron, [(i-Pr)3C5H2]2Fe, and bis(tetraisopropylcyclopentadienyl)iron, [(i-Pr)4C5H]2Fe, can be oxidized with NOBF4 to give the corresponding ferrocenium salts {[(i-Pr)3C5H2]2Fe}BF4 and {[(i-Pr)4C5H]2Fe}BF4 in high yield. Oxidation of [(i-Pr)3C5H2]2Co and [(i-Pr)4C5H]2Co with NH4X (X = [PF6]-, [BPh4]-) yields the cobaltocenium complexes {[(i-Pr)3C5H2]2Co}X and {[(i-Pr)4C5H]2Co}X. The oxidation of [(i-Pr)4C5H]2M (M = Fe or Co) is significantly slower than that for [(i-Pr)3C5H2]2M. The single-crystal X-ray structures of the neutral [(i-Pr)3C5H2]2M metallocenes and cationic {[(i-Pr)3C5H2]2M}+ and {[(i-Pr)4C5H]2M}+ metallocenes are reported. ...