Dinitrogen Reduction, Sulfur Reduction, and Isoprene Polymerization via Photochemical Activation of Trivalent Bis(cyclopentadienyl) Rare-Earth-Metal Allyl Complexes

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• 作者：Megan E. Fieser ; Casey W. Johnson ; Jefferson E. Bates ; Joseph W. Ziller ; Filipp Furche ; William J. Evans
• 刊名：Organometallics
• 出版年：2015
• 出版时间：September 14, 2015
• 年：2015
• 卷：34
• 期：17
• 页码：4387-4393
• 全文大小：378K
• ISSN：1520-6041

文摘

Dinitrogen can be reduced by photochemical activation of the trivalent rare-earth-metal bis(pentamethylcyclopentadienyl) allyl complexes (C₅Me₅)₂Ln(畏³-C₃H₄R) (Ln = Y, Lu; R = H, Me) to form the (N鈺怤)^{2鈥?/sup> complexes [(C₅Me₅)₂Ln]₂(渭-畏2:畏2-N₂). This demonstrates that productive organolanthanide photochemistry is not limited to complexes of the unusual (畏3-C₅Me₄H)鈭?/sup> ligand in the heteroleptic complexes (C₅Me₅)₂(C₅Me₄H)Ln and (C₅Me₅)(C₅Me₄H)₂Ln. Photolytic activation of (C₅Me₅)₂Ln(畏3-C₃H₅) (Ln = Y, Lu) in the presence of isoprene provides a rare photopolymerization route to polyisoprene. Sulfur can also be reduced by photolysis of (C₅Me₅)₂Ln(畏3-C₃H₅) (Ln = Y, Lu) to generate the (S)2鈥?/sup> complexes, [(C₅Me₅)₂Ln]₂(渭-S), which have variable Ln鈥揝鈥揕n angles depending on crystallization conditions.}