Evidence for the Existence of Group 3 Terminal Methylidene Complexes

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• 作者：Daniel S. Levine ; T. Don Tilley ; Richard A. Andersen
• 刊名：Organometallics
• 出版年：2017
• 出版时间：January 9, 2017
• 年：2017
• 卷：36
• 期：1
• 页码：80-88
• 全文大小：520K
• ISSN：1520-6041

文摘

Terminal group 3 methylidene complexes are generated by thermolysis of monoanionic PNP-supported scandium and yttrium dialkyl complexes. The reaction mechanism has been probed by deuterium-labeling experiments and DFT calculations. Abstraction of a γ-hydrogen from one alkyl group by the other affords a metallacyclobutane that undergoes [2 + 2] cycloreversion, analogous to a key step in the olefin metathesis reaction, to generate a methylidene complex and isobutene. The resulting methylidene complex dimerizes in the case of scandium and decomposes to a mixture of products in the case of yttrium.