Highly Congested Donor鈥揂cceptor P鈥揃 Compound: Synthesis and Properties of a BMes2- and a PPh2-Functionalized 1,8-Naphthalene

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• 作者：Yu-Fei Li ; Youngjin Kang ; Soo-Byung Ko ; Yingli Rao ; Francoise Sauriol ; Suning Wang
• 刊名：Organometallics
• 出版年：2013
• 出版时间：May 24, 2013
• 年：2013
• 卷：32
• 期：10
• 页码：3063-3068
• 全文大小：290K
• 年卷期：v.32,no.10(May 24, 2013)
• ISSN：1520-6041

文摘

A PPh₂- and BMes₂-functionalized (Mes = mesityl) 1,8-naphthalene molecule (1) has been synthesized and fully characterized. Compound 1 is a highly congested molecule with a P鈥揃 dative bond. NMR studies support that the P鈥揃 bond in 1 is persistent in solution. Compound 1 is thermally and photochemically stable. It is highly fluxional in solution. The only reactivity it displays is its reactions with halogen molecules (PhI路Cl₂ and I₂), leading to the isolation of a hydrolyzed product 2, in which an oxygen atom is inserted between the P and B atom. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction analyses. A DFT computational study established that the open form of 1 has a P鈥揃 separation distance of 3.00 脜, much longer than the closed one (2.23 脜). Furthermore, a computational study showed that the energy difference between the two forms is very small, 1 kcal/mol, which can be attributed to the highly congested nature of the molecule.