Cyclobutadieneiron Tricarbonyl Annelated with Homoadamantene Frameworks

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• 作者：Shinya Minegishi ; Koichi Komatsu ; Toshikazu Kitagawa
• 刊名：Organometallics
• 出版年：2011
• 出版时间：March 14, 2011
• 年：2011
• 卷：30
• 期：5
• 页码：1002-1007
• 全文大小：874K
• 年卷期：v.30,no.5(March 14, 2011)
• ISSN：1520-6041

文摘

Cyclobutadieneiron tricarbonyl annelated with homoadamantene 2 was synthesized from the corresponding 3,4-dibromocyclobutene 8. As a stable cationic analogue of 2, the dicarbonyl nitrosyl complex 3⁺ was also prepared. X-ray crystallographic studies revealed that the homoadamantene units of both 2 and 3⁺ are highly bent out of the cyclobutadiene ring plane away from Fe. The cyclobutadiene units in 2 and 3⁺ are significantly distorted to a rectangular shape, which made the transannular carbon鈭抍arbon bonds shorter than the other two. An enhanced donor ability of the cyclobutadiene unit was suggested by X-ray crystallography, infrared spectra, and DFT calculations. In accordance with this, reversible oxidation waves were observed in the cyclic voltammogram of 2, reflecting an enhanced stability of the oxidized form.