1. Theoretical Aspects of Compounds Containing Si, Ge, Sn and Pb

  1. Zvi Rappoport4 and
  2. Yitzhak Apeloig5
  1. Miriam Karni1,
  2. Yitzhak Apeloig1,
  3. Jürgen Kapp2 and
  4. Paul von R. Schleyer2,†

Published Online: 18 JUL 2003

DOI: 10.1002/0470857269.ch1

The Chemistry of Organic Silicon Compounds, Volume 3

The Chemistry of Organic Silicon Compounds, Volume 3

How to Cite

Karni, M., Apeloig, Y., Kapp, J. and Schleyer, P. v. R. (2001) Theoretical Aspects of Compounds Containing Si, Ge, Sn and Pb, in The Chemistry of Organic Silicon Compounds, Volume 3 (eds Z. Rappoport and Y. Apeloig), John Wiley & Sons, Ltd, Chichester, UK. doi: 10.1002/0470857269.ch1

Editor Information

  1. 4

    The Hebrew University, Jerusalem, Israel

  2. 5

    Israel Institute of Technology, Haifa, Israel

Author Information

  1. 1

    Department of Chemistry, and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel. Fax: 972-4-8294601

  2. 2

    Computer Chemistry Center of the Institute of Organic Chemistry, The University of Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany

  1. Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602-2525, USA. Fax: 706 542-7514

Publication History

  1. Published Online: 18 JUL 2003
  2. Published Print: 10 DEC 2001

Book Series:

  1. PATAI'S Chemistry of Functional Groups

Book Series Editors:

  1. Zvi Rappoport

Series Editor Information

  1. The Hebrew University, Jerusalem, Israel

ISBN Information

Print ISBN: 9780471623847

Online ISBN: 9780470857267

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Summary

This chapter contains sections titled:

  • List of Abbreviations

  • Introduction

  • Periodic Trends in the Properties of Group 14 Elements

    • Radial Orbital Extensions

    • Relativistic Effects

    • Hybridization

    • Electronegativity and Bonding

    • Spin–Orbit Coupling

    • The Role of d Orbitals

  • Theoretical Methods

    • Nonrelativistic Theoretical Methods

    • Relativistic Methods

    • Effective Core Potential Basis Sets

    • Methods for Analysis of the Electronic Structure

  • Singly Bonded Compounds

    • MH4 (Metallanes)

      • Geometries, Ionization Potentials and Nuclear Spin–Spin Couplings

      • Bond Energies

      • The Stability of MH4 Relative to MH2 + H2

      • Charged MH4 Species: MH4+ and MH42+

    • Mono-substituted Singly-bonded MH3R Metallanes

      • General Trends in the M[BOND]R Bond Dissociation Energies

      • MH3R, R = Halogen

        • Geometries

        • M[BOND]R Bond Dissociation Energies

      • Ethane Analogs

        • Geometries and Rotational Barriers

        • Bond Dissociation Energies

        • Nonclassical Bridged Structures of Ethane Analogs

      • Classical Linear MnH2n + 2 Chains

    • Multiply-substituted Singly-bonded Compounds

      • M(CH3)4 and MX4, X = Halogen

      • (CH3)nMX4 – n

      • Relative Stabilities of MIV and MII Compounds

      • Oxides and Sulfides

      • MLi4

    • Hypercoordinated Systems

      • MH5

      • MX5, X = Alkali Metals

      • MX6, MX7 and MX8, X = Alkali Metals

    • Cyclic Metallanes: Rings, Polycyclic and Polyhedral Compounds

      • Saturated Ring Compounds

        • c-M3H6 and c-M4H8

          • Structures

          • Strain

          • Stability Towards Cleavage

          • Other Structures of 3-MRs

        • Metalloles

        • Heterocyclic 3- and 4-membered Rings

          • 3-MRs, c-(R2M)2X

          • 1,3-Dioxa-2,4-dimetaletanes, c-(MH2)2O2

      • Polycyclic and Polyhedral Metallanes

        • Bicyclic Compounds

        • Propellanes

        • Polyhedral Cage Compounds: Tetrahedrane, Prismane, Cubane and Larger MnHn Systems

        • Polyhedral Metallaboranes

  • Multiply-bonded Systems

    • Historical Overview

    • M[DOUBLE BOND]M′ Doubly-bonded Compounds (Metallenes)

      • Structures

      • The Double-bond Strength

      • Stability Relative to Isomeric Structures

        • Relative to the Corresponding Metallylenes

        • Relative to Bridged Isomers

          • Hydrogen Bridged Isomers

          • π-donor Bridged Isomers

    • R2[DOUBLE BOND]MX Compounds

      • Structures and Bond Energies

      • Isomerization to Metallylenes

    • Increasing the Number of Double Bonds

      • Heavier Analogs of 1,3-butadiene

      • Heavier Analogs of Allene

    • Triply-bonded Metallanes, RM[TRIPLE BOND]M′R′

      • Structures and Bond Nature

      • Potential Energy Surfaces

        • HC[TRIPLE BOND]MH, M = Si, Ge

        • HM[TRIPLE BOND]MH and HM[TRIPLE BOND]M′H

    • Aromatic Compounds

      • The Congeners of Benzene and Their Isomers

      • Metallacyclopropenium Cations

      • Metallacyclopentadienyl Anion and Dianion

      • Metallocenes

  • Reactive Intermediates

    • Divalent Compounds (Metallylenes)

      • MH2 and MX2 (X = Halogen)

      • Stable Metallylenes

      • Reactions

        • 1,2-hydrogen Shifts

        • Insertion and Addition Reactions

          • Insertion into H2

          • Insertion into M[BOND]H Bonds

          • Insertion into X[BOND]H σ-bonds

          • Addition to Double Bonds

          • Addition to Acetylene

    • Tricoordinated Compounds

      • Tricoordinated Cations

        • Structures

        • Thermodynamic and Kinetic Stability of MR3+ Cations

      • Tricoordinated Radicals

      • Tricoordinated Anions

    • Pentacoordinated Compounds

      • Pentacoordinated Cations

      • Pentacoordinated Radicals

      • Pentacoordinated Anions

  • Conclusions and Outlook

  • Acknowledgments

  • References