Circumambulatory Rearrangement with Characteristics of a 2:1 Covalent Molecular Bevel Gear

详细信息    查看全文

• 作者：Rosa E. Bulo ; Florian Allaart ; Andreas W. Ehlers ; Franciscus J. J. de Kanter ; Marius Schakel ; Martin Lutz ; Anthony L. Spek ; Koop Lammertsma
• 刊名：Journal of the American Chemical Society
• 出版年：2006
• 出版时间：September 20, 2006
• 年：2006
• 卷：128
• 期：37
• 页码：12169 - 12173
• 全文大小：164K
• 年卷期：v.128,no.37(September 20, 2006)
• ISSN：1520-5126

文摘

anti-W(CO)₅-complexed 9-methyl-9-phosphabicyclo[6.1.0]nonatriene represents a covalentlyinterlocked molecular bevel gear. Correlated movement of the phosphorus atom and the eight-memberedring by way of a "walk" rearrangement makes gear slippage impossible. The gearing motion is transferredto the four-toothed W(CO)₅ propeller connected to the rotating phosphorus atom, enabling a gearing ratioof 2:1 according to B3LYP and Car-Parrinello Molecular Dynamics calculations. Methyl substitution of theeight-membered ring tempers the gearing process, with the PMeW(CO)₅ entity passing the substitutedcarbon atom only at temperatures above 50 es/entities/deg.gif">C