Chapter 10-Silicenium Ions - Quantum Chemical Computations (p 513-555).pdfVIP

The Chemistry of Organic Silicon Compounds. Volume 2 Edited by Zvi Rappoport and Yitzhak Apeloig Copyright 1998 John Wiley Sons, Ltd. ISBN: 0-471-96757-2 CHAPTER 10 Silicenium ions: Quantum chemical computations ′ ? CHRISTOPH MAERKER and PAUL VON RAGUE SCHLEYER Computer Chemistry Center of the Institute of Organic Chemistry, The University of Erlangen-Nurnberg, Henkestrasse 42, 91054 Erlangen, Germany ¨ Fax: 49-9131-85-9132, e-mail: pvrs@ccc.uni-erlangen.de I. ABBREVIATIONS . 514 II. INTRODUCTION . . 514 III. COMPUTATIONAL METHODS . . 515 A. ‘Traditional’ ab initio Molecular Orbital MO Techniques . . . 515 B. Density Functional Theory DFT Based Methods . . . . 516 C. Computations of Magnetic Properties . . 516 IV. QUANTUM MECHANICAL STUDIES OF SILICENIUM CATIONS . . 517 A. Thermodynamic Stability of Silicenium Cations 517 B. Towards Free Silicenium Ions in Solution: How Can They be Prepared . 519 C. Trialkyl-substituted Silicenium Ions . . . 520 1. Energetic stabilization by multiple alkyl substitution 520 2. The ?rst X-ray structures: The ?rst stable tricoordinate silicenium ions . . 520 3. Interactions with Lewis bases: Binary and ternary complexes . . . . 524 D. 29 Si NMR Chemical Shifts of Silicenium Ions . 532 E. -Donor Stabilized Silicenium Ions . . . 538 1. The silaguanidinium ion . . . . 538 2. Resonance stabilization by aromatic substituents . . . 540 3. Intramolecular -stabilization 543 F. Stabilization by Organoboryl Groups . . 547 V. CONCLUDING REMARKS AND OUTLOOK . . . 550 VI. REFERENCES . . . . 551 ? New postal address: Center for Computational Quantum Chemistry The University of Georgia, Athens, GA 30602 USA. Fax: C1-706-542-0406 513 514 Christoph Maerker and Paul von Rague Schleyer ′ I. ABBREVIATIONS B Becke’s exchange functional B3LYP three-parameter hybrid exchange-correlation-density functional BII standard basis set of triple-zeta quality, including polarization functions for all elements, of