J. Am. Chem. Soc., ASAP Article 10.1021/ja057085u S0002-7863(05)07085-X
Web Release Date: June 10, 2006
Copyright © 2006 American Chemical Society
Electronic Properties of Furyl Substituents at Phosphorus and Their Influence on 31P NMR Chemical Shifts
Marco Ackermann, Aurelia Pascariu, Thomas Höcher, Hans-Ullrich Siehl, and Stefan Berger*
Contribution from the Institut für Analytische Chemie, Fakultät für Chemie und Mineralogie, Universität Leipzig, Linnéstr. 3, D-04103 Leipzig, Germany and Abteilung für Organische Chemie I, Fakultät für Naturwissenschaften, Universität Ulm, D-89069 Ulm, Germany
The electronic properties of 2-furyl and 3-furyl substituents attached to phosphanes and phosphonium salts were studied by means of IR spectroscopy and experimental and computational 31P NMR spectroscopy. The heteroaromatic systems proved to be electron withdrawing with respect to phenyl substituents. However, phosphorus atoms with attached furyl substituents are strongly shielded in NMR. The reason for this phenomenon was studied by solid state 31P MAS NMR experiments. The chemical shift tensor was extracted, and the orientation within the molecules was determined. The tensor component 33, which is effected the most by furyl systems, is oriented perpendicular to the P-C bonds of the substituents. P-furyl bonds are shorter than P-phenyl bonds. We assume therefore a lower ground-state energy of the molecules, because of the electron withdrawing properties of the 2-furyl systems. The para component of the 31P NMR magnetic shielding is therefore smaller, which results in an overall increase of the magnetic shielding.