Synthesis, Structures, and Properties of 'Encapsulated' Iron and Cobalt Metallocenes with Highly Isopropylated Cyclopentadienyl Rings
| Autor: | Melanie L. Hays, Timothy P. Hanusa, and Randall E. Duderstadt, David J. Burkey |
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| Rok vydání: | 1997 |
| Předmět: | |
| Zdroj: | Organometallics. 16:1465-1475 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om960740+ |
| Popis: | 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. ... |
| Databáze: | OpenAIRE |
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