Intramolecularly Coordinated (6-(Diphenylphosphino)acenaphth-5-yl)stannanes. Repulsion vs Attraction of P- and Sn-Containing Substituents in the peri Positions

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• 作者：Emanuel Hupf ; Enno Lork ; Stefan Mebs ; Jens Beckmann
• 刊名：Organometallics
• 出版年：2014
• 出版时间：May 27, 2014
• 年：2014
• 卷：33
• 期：10
• 页码：2409-2423
• 全文大小：701K
• 年卷期：v.33,no.10(May 27, 2014)
• ISSN：1520-6041

文摘

The intramolecularly coordinated (6-(diphenylphosphino)acenaphth-5-yl)stannanes ArSnBu₃ (1), ArSnPh₃ (2), ArSnPh₂Cl (3), ArSnPhCl₂ (4), ArSnCl₃ (5), Ar₂SnCl₂ (6), ArSnPh₂O₃SCF₃ (7), and ArSnPh₂F (8) were synthesized and fully characterized by multinuclear NMR spectroscopy (¹¹⁹Sn, ³¹P, ¹⁹F, ¹³C, ¹H) and X-ray crystallography (Ar = 6-Ph₂P-Ace-5-). Due to the different substituents, the Lewis acidities of the Sn atoms of 1鈥?b>8 vary substantially, which is reflected in the different P鈥揝n peri distances lying in the range from 2.7032(9) to 3.332(2) 脜. In MeCN, 7 undergoes electrolytic dissociation into solvated triarylstannyl cations and triflate anions. The gas-phase structures of 2鈥?b>5, 8, and the triarylstannyl cations ArPh₂Sn⁺ (7a) and [ArPh₂Sn路NCMe]⁺ (7b) were obtained by geometry optimization at the B3PW91/TZ level of theory. A detailed analysis of a set of real-space bonding indicators (RSBI) derived from the electron and pair densities following the atoms in molecules (AIM) and electron localizability indicator (ELI-D) topological approaches, respectively, uncovers the Sn鈥揚 peri interaction in 2 to be in the border regime between nonbonding and weakly ionic. With an increasing number of Cl atoms attached to the Sn atom, the Sn鈥揚 bond becomes considerably shorter and exhibits a decreasingly polar covalent interaction. As expected, this trend is significantly enhanced for the Sn鈥揚 interactions in the charged compounds 7a,b. The Sn鈥揚 bond properties of 8, however, very much resemble those of 3, which means that the electronic impact of the F atom in the axial position is comparable to that of the axial Cl atom.