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19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes

✍ Scribed by Ion Ghiviriga; Lianhao Zhang; Henry Martinez; Rubén H. Contreras; Cláudio F. Tormena; Laura Nodin; William R. Dolbier Jr

Publisher
John Wiley and Sons
Year
2011
Tongue
English
Weight
485 KB
Volume
49
Category
Article
ISSN
0749-1581

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✦ Synopsis

Abstract

In the process of studying the chemistry of perfluoro[2.2]paracyclophanes (PFPCs), a novel class of compounds, it became necessary to identify some disubstituted products. To achieve this goal, we characterize in this work some monosubstituted PFPCs, identifying their ^19^F^19^F coupling patterns, and establishing a methodology for the assignment of their ^19^F chemical shifts. The pattern of coupling constants indicates a skewed geometry in which the upper deck moves towards or away from the substituent, depending on the substituent electron‐donor character and size. Quantum chemical calculations, performed at the HF/6‐311 + G(d,p)//B3LYP/EPR‐III level of theory, confirmed the conformations inferred from coupling constants and reproduced well the values of the couplings. Transmission mechanisms for the FC term of four‐ and five‐bond ^19^F^19^F couplings are discussed in detail. Understanding the conformational preferences of PFPCs and how they are reflected by the coupling constants facilitates the assignment of ^19^F chemical shifts in monosubstituted PFPCs and the identification of the disubstituted products. Copyright © 2011 John Wiley & Sons, Ltd.

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