The Chemistry of Organic Germanium Tin and Lead Compounds Vol-1-1995-Patai

The chemistry oforganic germanium, tinand lead compounds

The Chemistry of Organic Germanium, Tin and Lead Compounds. Volume 1Edited by Saul Patai

Copyright 1995 John Wiley & Sons, Ltd.ISBN: 0-471-94207-3

THE CHEMISTRY OF FUNCTIONAL GROUPSA series of advanced treatises under the general editorship of

Professors Saul Patai and Zvi RappoportThe chemistry of alkenes (2 volumes)

The chemistry of the carbonyl group (2 volumes)The chemistry of the ether linkageThe chemistry of the amino group

The chemistry of the nitro and nitroso groups (2 parts)The chemistry of carboxylic acids and esters

The chemistry of the carbon nitrogen double bondThe chemistry of amides

The chemistry of the cyano groupThe chemistry of the hydroxyl group (2 parts)

The chemistry of the azido groupThe chemistry of acyl halides

The chemistry of the carbon halogen bond (2 parts)The chemistry of the quinonoid compounds (2 volumes, 4 parts)

The chemistry of the thiol group (2 parts)The chemistry of the hydrazo, azo and azoxy groups (2 parts)

The chemistry of amidines and imidates (2 volumes)The chemistry of cyanates and their thio derivatives (2 parts)

The chemistry of diazonium and diazo groups (2 parts)The chemistry of the carbon carbon triple bond (2 parts)

The chemistry of ketenes, allenes and related compounds (2 parts)The chemistry of the sulphonium group (2 parts)

Supplement A: The chemistry of double-bonded functional groups (2 volumes, 4 parts)Supplement B: The chemistry of acid derivatives (2 volumes, 4 parts)

Supplement C: The chemistry of triple-bonded functional groups (2 volumes, 3 parts)Supplement D: The chemistry of halides, pseudo-halides and azides (2 volumes, 4 parts)

Supplement E: The chemistry of ethers, crown ethers, hydroxyl groups and their sulphur analogues(2 volumes, 3 parts)

Supplement F: The chemistry of amino, nitroso and nitro compounds and their derivatives (2 parts)The chemistry of the metal carbon bond (5 volumes)

The chemistry of peroxidesThe chemistry of organic selenium and tellurium compounds (2 volumes)

The chemistry of the cyclopropyl group (2 parts)The chemistry of sulphones and sulphoxides

The chemistry of organic silicon compounds (2 parts)The chemistry of enones (2 parts)

The chemistry of sulphinic acids, esters and their derivativesThe chemistry of sulphenic acids and their derivatives

The chemistry of enolsThe chemistry of organophosphorus compounds (3 volumes)The chemistry of sulphonic acids, esters and their derivatives

The chemistry of alkanes and cycloalkanesSupplement S: The chemistry of sulphur-containing functional groupsThe chemistry of organic arsenic, antimony and bismuth compounds

The chemistry of enamines (2 parts)The chemistry of organic germanium, tin and lead compounds

UPDATESThe chemistry of -haloketones, -haloaldehydes and -haloimines

Nitrones, nitronates and nitroxidesCrown ethers and analogs

Cyclopropane derived reactive intermediatesSynthesis of carboxylic acids, esters and their derivatives

The silicon heteroatom bondSyntheses of lactones and lactams

The syntheses of sulphones, sulphoxides and cyclic sulphidesPatais 1992 guide to the chemistry of functional groups Saul Patai

C Ge, C Sn, C Pb

The chemistry oforganic germanium, tinand lead compounds

Edited bySAUL PATAI

The Hebrew University, Jerusalem

1995

JOHN WILEY & SONSCHICHESTER NEW YORK BRISBANE TORONTO SINGAPORE

An Interscience R Publication

Copyright 1995 by John Wiley & Sons Ltd,Baffins Lane, Chichester,West Sussex PO19 1UD, England

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Library of Congress Cataloging-in-Publication DataThe chemistry of organic germanium, tin, and lead compounds / edited

by Saul Patai.p. cm. (The chemistry of functional groups)

An Interscience publication.Includes bibliographical references (p. - ) and index.ISBN 0-471-94207-3 (alk. paper)1. Organogermanium compounds. 2. Organotin compounds.

3. Organolead compounds. I. Patai, Saul. II. Series.QD412.G5C47 1995547.050684 dc20 95-19750

CIP

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ISBN 0 471 94207 3

Typeset in 9/10pt Times by Laser Words, Madras, IndiaPrinted and bound in Great Britain by Biddles Ltd, Guildford, SurreyThis book is printed on acid-free paper responsibly manufactured from sustainable forestation, forwhich at least two trees are planted for each one used for paper production.

Contributing authorsHarold Basch Department of Chemistry, Bar-Ilan University, Ramat-

Gan 52900, IsraelCarla Cauletti Dipartimento di Chimica, Universita` di Roma La

Sapienza, Piazzale Aldo Moro 5, 00185 Roma, ItalyMarvin Charton Chemistry Department, School of Liberal Arts and

Sciences, Pratt Institute, Brooklyn, New York 11205,USA

Peter J. Craig Department of Chemistry, School of Applied Sciences,De Montfort University, The Gateway, Leicester,LE1 9BH, UK

J. T. van Elteren Department of Chemistry, School of Applied Sciences,De Montfort University, The Gateway, Leicester, LE19BH, UK

Marcel Gielen Faculty of Applied Sciences, Free University of Brussels,Room 8G512, Pleinlaan 2, B-1050 Brussels, Belgium

Charles M. Gordon School of Chemical Sciences, Dublin City University,Dublin 9, Ireland

Sarina Grinberg Institutes for Applied Research, Ben-Gurion Universityof the Negev, Beer-Sheva 84110, Israel

Tova Hoz Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel

L. M. Ignatovich Latvian Institute of Organic Synthesis, Riga, LV 1006Latvia

Jim Iley Physical Organic Chemistry Research Group, ChemistryDepartment, The Open University, Milton Keynes,MK7 6AA, UK

Jill A. Jablonowski Department of Chemistry and Biochemistry, Universityof South Carolina, Columbia, South Carolina 29208,USA

Helen Joly Department of Chemistry, Laurentian University, Sud-bury, Ontario P3E 2C6, Canada

Thomas M. Klapotke Institut fur Anorganische und Analytische Chemie,Technische Universitat Berlin, Strasse des 17 Juni 135,D-10623 Berlin, Germany

Joel F. Liebman Department of Chemistry and Biochemistry, Universityof Maryland, Baltimore County, 5401 Wilkens Avenue,Baltimore, Maryland 21228-5398, USA

v

vi Contributing authors

Conor Long School of Chemical Sciences, Dublin City University,Dublin 9, Ireland

E. Lukevics Latvian Institute of Organic Synthesis, Riga, LV 1006Latvia

Kenneth M. Mackay School of Science and Technology, University of Waikato,P.B. 3105, Hamilton, New Zealand

Shigeru Maeda Department of Applied Chemistry and Chemical Engin-eering, Faculty of Engineering, Kagoshima University,1-21-40 Korimoto, Kagoshima 890, Japan

James A. Marshall Department of Chemistry and Biochemistry, Universityof South Carolina, Columbia, South Carolina 29208,USA

Michael Michman Department of Organic Chemistry, The Hebrew Univer-sity of Jerusalem, Jerusalem 91904, Israel

Axel Schulz Institut fur Anorganische und Analytische Chemie,Technische Universitat Berlin, Strasse des 17 Juni 135,D-10623 Berlin, Germany

Larry R. Sherman Department of Chemistry, University of Scranton, Scran-ton, Pennsylvania 18519-4626, USA

Jose A. Martinho Simoes Departamento de Qumica, Faculdade de Ciencias,Universidade de Lisboa, 1700 Lisboa, Portugal

Suzanne W. Slayden Department of Chemistry, George Mason University,4400 University Drive, Fairfax, Virginia 22030-4444,USA

Stefano Stranges Dipartimento di Chimica, Universita` di Roma LaSapienza, Piazzale Aldo Moro 5, 00185 Roma, Italy

John M. Tsangaris Department of Chemistry, University of Ioannina,GR-45100 Ioannina, Greece

Kenneth C. Westaway Department of Chemistry, Laurentian University, Sud-bury, Ontario P3E 2C6, Canada

Rudolph Willem Faculty of Applied Sciences, Free University of Brussels,Room 8G512, Pleinlaan 2, B-1050 Brussels, Belgium

Jacob Zabicky Institutes for Applied Research, Ben-Gurion Universityof the Negev, Beer-Sheva 84110, Israel

ForewordAs was the case with the volume The chemistry of organic arsenic, antimony and bis-muth compounds, published in 1994, it was clear that the set of five volumes describingorganometallic compounds (edited by Professor Frank R. Hartley) did not deal in suffi-cient depth with organic compounds of germanium, tin and lead. Hence we decided topublish the present volume, which we hope will be a useful and worthwhile additionto the series The Chemistry of Functional Groups. In this volume the authors literaturesearch extended in most cases up to the end of 1994.

The following chapters unfortunately did not materialize: Mass spectra; NMR andMossbauer spectroscopy; Organic Ge, Sn and Pb compounds as synthones; Ge, Sn andPb analogs of radicals and of carbenes; and Rearrangements. Moreover, the volume doesnot contain a classical chapter on biochemistry, although much of the relevant material isincluded in the chapter on environmental methylation of Ge, Sn and Pb and in the chapteron the toxicity of organogermanium compounds, in the chapter on organotin toxicologyand also in the chapter on safety and environmental effects.

I hope that the above shortcomings will be amended in one of the forthcoming supple-mentary volumes of the series.

I will be indebted to readers who will bring to my attention mistakes or omissions inthis or in any other volume of the series.

Jerusalem SAUL PATAIMay 1995

vii

The Chemistry of Functional GroupsPreface to the series

The series The Chemistry of Functional Groups was originally planned to cover ineach volume all aspects of the chemistry of one of the important functional groups inorganic chemistry. The emphasis is laid on the preparation, properties and reactions of thefunctional group treated and on the effects which it exerts both in the immediate vicinityof the group in question and in the whole molecule.

A voluntary restriction on the treatment of the various functional groups in thesevolumes is that material included in easily and generally available secondary or ter-tiary sources, such as Chemical Reviews. Quarterly Reviews, Organic Reactions, variousAdvances and Progress series and in textbooks (i.e. in books which are usually foundin the chemical libraries of most universities and research institutes), should not, as a rule,be repeated in detail, unless it is necessary for the balanced treatment of the topic. There-fore each of the authors is asked not to give an encyclopaedic coverage of his subject,but to concentrate on the most important recent developments and mainly on material thathas not been adequately covered by reviews or other secondary sources by the time ofwriting of the chapter, and to address himself to a reader who is assumed to be at a fairlyadvanced postgraduate level.

It is realized that no plan can be devised for a volume that would give a complete cov-erage of the field with no overlap between chapters, while at the same time preserving thereadability of the text. The Editors set themselves the goal of attaining reasonable coveragewith moderate overlap, with a minimum of cross-references between the chapters. In thismanner, sufficient freedom is given to the authors to produce readable quasi-monographicchapters.

The general plan of each volume includes the following main sections:(a) An introductory chapter deals with the general and theoretical aspects of the group.(b) Chapters discuss the characterization and characteristics of the functional groups,

i.e. qualitative and quantitative methods of determination including chemical and physicalmethods, MS, UV, IR, NMR, ESR and PES as well as activating and directive effectsexerted by the group, and its basicity, acidity and complex-forming ability.

(c) One or more chapters deal with the formation of the functional group in question,either from other groups already present in the molecule or by introducing the new groupdirectly or indirectly. This is usually followed by a description of the synthetic uses ofthe group, including its reactions, transformations and rearrangements.

(d) Additional chapters deal with special topics such as electrochemistry, photochem-istry, radiation chemistry, thermochemistry, syntheses and uses of isotopically labelledcompounds, as well as with biochemistry, pharmacology and toxicology. Whenever appli-cable, unique chapters relevant only to single functional groups are also included (e.g.Polyethers, Tetraaminoethylenes or Siloxanes).

ix

x Preface to the series

This plan entails that the breadth, depth and thought-provoking nature of each chapterwill differ with the views and inclinations of the authors and the presentation will neces-sarily be somewhat uneven. Moreover, a serious problem is caused by authors who delivertheir manuscript late or not at all. In order to overcome this problem at least to someextent, some volumes may be published without giving consideration to the originallyplanned logical order of the chapters.

Since the beginning of the Series in 1964, two main developments have occurred.The first of these is the publication of supplementary volumes which contain materialrelating to several kindred functional groups (Supplements A, B, C, D, E, F and S). Thesecond ramification is the publication of a series of Updates, which contain in eachvolume selected and related chapters, reprinted in the original form in which they werepublished, together with an extensive updating of the subjects, if possible, by the authorsof the original chapters. A complete list of all above mentioned volumes published todate will be found on the page opposite the inner title page of this book. Unfortunately,the publication of the Updates has been discontinued for economic reasons.

Advice or criticism regarding the plan and execution of this series will be welcomedby the Editors.

The publication of this series would never have been started, let alone continued,without the support of many persons in Israel and overseas, including colleagues, friendsand family. The efficient and patient co-operation of staff-members of the publisher alsorendered us invaluable aid. Our sincere thanks are due to all of them.

The Hebrew University SAUL PATAIJerusalem, Israel ZVI RAPPOPORT

Contents1. The nature of the CM bond (M D Ge, Sn, Pb) 1

Harold Basch and Tova Hoz

2. Structural aspects of compounds containing CE (E D Ge, Sn,Pb) bonds 97

Kenneth M. Mackay

3. Stereochemistry and conformation of organogermanium, organotinand organolead compounds 195

James A. Marshall and Jill A. Jablonowski

4. Thermochemistry of organometallic compounds of germanium, tinand lead 245

Jose A. Martinho Simoes, Joel F. Liebman and SuzanneW. Slayden

5. ESR of organogermanium, organotin and organolead radicals 267Jim Iley

6. Photoelectron spectroscopy (PES) of organometallic compoundswith CM (M D Ge, Sn, Pb) bonds 291

Carla Cauletti and Stefano Stranges

7. Analytical aspects of organogermanium compounds 339Jacob Zabicky and Sarina Grinberg

8. Analytical aspects of organotin compounds 365Jacob Zabicky and Sarina Grinberg

9. Analytical aspects of organolead compounds 429Jacob Zabicky and Sarina Grinberg

10. Synthesis of M(IV) organometallic compounds where M D Ge,Sn, Pb 453

John M. Tsangaris, Rudolph Willem and Marcel Gielen

11. Acidity, complexing, basicity and H-bonding of organic germanium,tin and lead compounds: experimental and computational results 537

Axel Schulz and Thomas A. Klapotke

xi

xii Contents

12. Substituent effects of germanium, tin and lead groups 603Marvin Charton

13. The electrochemistry of alkyl compounds of germanium, tinand lead 665

Michael Michman

14. The photochemistry of organometallic compounds of germanium,tin and lead 723

Charles M. Gordon and Conor Long

15. Syntheses and uses of isotopically labelled organic derivatives ofGe, Sn and Pb 759

Kenneth C. Westaway and Helen Joly

16. The environmental methylation of germanium, tin and lead 843P. J. Craig and J. T. van Elteren

17. Toxicity of organogermanium compounds 857E. Lukevics and L. M. Ignatovich

18. Organotin toxicology 865Larry R. Sherman

19. Safety and environmental effects 871Shigeru Maeda

Author index 911

Subject index 975

List of abbreviations usedAc acetyl (MeCO)acac acetylacetoneAd adamantylAIBN azoisobutyronitrileAlk alkylAll allylAn anisylAr aryl

Bz benzoyl (C6H5CO)Bu butyl (also t-Bu or But )

CD circular dichroismCI chemical ionizationCIDNP chemically induced dynamic nuclear polarizationCNDO complete neglect of differential overlapCp 5-cyclopentadienylCp 5-pentamethylcyclopentadienyl

DABCO 1,4-diazabicyclo[2.2.2]octaneDBN 1,5-diazabicyclo[4.3.0]non-5-eneDBU 1,8-diazabicyclo[5.4.0]undec-7-eneDIBAH diisobutylaluminium hydrideDME 1,2-dimethoxyethaneDMF N , N -dimethylformamideDMSO dimethyl sulphoxide

ee enantiomeric excessEI electron impactESCA electron spectroscopy for chemical analysisESR electron spin resonanceEt ethyleV electron volt

xiii

xiv List of abbreviations used

Fc ferrocenylFD field desorptionFI field ionizationFT Fourier transformFu furyl(OC4H3)

GLC gas liquid chromatography

Hex hexyl(C6H13)c-Hex cyclohexyl(C6H11)HMPA hexamethylphosphortriamideHOMO highest occupied molecular orbitalHPLC high performance liquid chromatography

i- isoIp ionization potentialIR infraredICR ion cyclotron resonance

LAH lithium aluminium hydrideLCAO linear combination of atomic orbitalsLDA lithium diisopropylamideLUMO lowest unoccupied molecular orbital

M metalM parent moleculeMCPBA m-chloroperbenzoic acidMe methylMNDO modified neglect of diatomic overlapMS mass spectrum

n normalNaph naphthylNBS N -bromosuccinimideNCS N -chlorosuccinimideNMR nuclear magnetic resonance

Pc phthalocyaninePen pentyl(C5H11)Pip piperidyl(C5H10N)Ph phenylppm parts per millionPr propyl (also i -Pr or Pri )PTC phase transfer catalysis or phase transfer conditionsPyr pyridyl (C5H4N)

List of abbreviations used xv

R any radicalRT room temperature

s- secondarySET single electron transferSOMO singly occupied molecular orbital

t- tertiaryTCNE tetracyanoethyleneTFA trifluoroacetic acidTHF tetrahydrofuranThi thienyl(SC4H3)TLC thin layer chromatographyTMEDA tetramethylethylene diamineTMS trimethylsilyl or tetramethylsilaneTol tolyl(MeC6H4)Tos or Ts tosyl(p-toluenesulphonyl)Trityl triphenylmethyl(Ph3C)

Xyl xylyl(Me2C6H3)

In addition, entries in the List of Radical Names in IUPAC Nomenclature of OrganicChemistry, 1979 Edition. Pergamon Press, Oxford, 1979, p. 305 322, will also be usedin their unabbreviated forms, both in the text and in formulae instead of explicitly drawnstructures.

CHAPTER 1

The nature of the CM bond(M=Ge, Sn, Pb)

HAROLD BASCH and TOVA HOZDepartment of Chemistry, Bar-Ilan University, Ramat-Gan 52900, IsraelFax: +(972)-3-535-1250; e-mail: [email protected]

I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2II. ATOMIC PROPERTIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

III. CALCULATIONAL METHODS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5IV. STRUCTURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

A. XH4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49B. XH3A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50C. XH3AH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51D. XH3AH2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52E. XH3AH3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54F. XH3AB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55G. XH3ABH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58H. XH3ABH3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60I. XH3ABH5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63J. XH3ABC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

K. XH3ABCH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71L. XH3ABCH2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

M. XH3ABCH3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73N. XH3ABCD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75O. XH3ABCDH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78P. XH3ABCDH3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79

V. BOND DISSOCIATION ENERGIES . . . . . . . . . . . . . . . . . . . . . . . . . 81A. XH4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85B. XH3A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85C. XH3AH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86D. XH3AH2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86E. XH3AH3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86F. XH3AB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87G. XH3ABH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88H. XH3ABH3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88I. XH3ABH5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89

1

The Chemistry of Organic Germanium, Tin and Lead Compounds. Volume 1Edited by Saul Patai

Copyright 1995 John Wiley & Sons, Ltd.ISBN: 0-471-94207-3

2 Harold Basch and Tova Hoz

J. XH3ABC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89K. XH3ABCH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89L. XH3ABCH2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

M. XH3ABCH3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90N. XH3ABCD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90O. XH3ABCDH3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

VI. REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

I. INTRODUCTIONThe nature of the carbon M bond as a function of the metal (M) atoms Ge, Sn and Pbhas been traditionally described using differences in the atomic properties of these atomsto explain trends in molecular bonding characteristics such as bond distances, angles andenergy properties. Emphasis has been on a comparison of properties contrasting behaviorrelative to carbon and silicon bonding to C, and among the metals themselves. Theimportance of relativistic effects in determining the properties of the heavier metal ligandbonds has also been extensively addressed.

The ability of the lightest of the Group 14 atoms, the carbon atom, to bind in so manyways with carbon and with other atoms in the Periodic Table attracts extensive comparisonwith the analogous compounds of Si, Ge, Sn and Pb, both real and hypothetical. The widerthe comparison, the greater the opportunity to gain insight into the secrets of chemicalbinding involving the Group 14 atoms, and to detect the nuances that differentiate theirproperties. Some of the causes of the differences are large, obvious and consistent. Othercauses are more subtle and difficult to identify. A combination of contrary trends caneffectively mask their individual characters when the individual effects are small.

The most obvious property to examine for trends and their causes is geometric struc-ture. Historically, bond lengths and bond angles in molecules were used to elucidateelectronic structure trends and construct descriptions of chemical bonding1. The majorobstacle hindering this approach is the general lack of a sufficiently large number andvariety of experimentally known molecular structures. Happily, recent developments inab initio electronic structure theory have provided chemists with the tools for accuratelycalculating geometric structures for ever-increasing sizes of molecules2. At the same time,developments in relativistic effective core potentials (RCEP)3 have allowed the incorpo-ration of both direct and indirect radial scaling effects due to relativistic properties of thecore electrons in the heavier atoms into the electronic structure description of their valenceelectrons. As has been known for some time already, certain differences in chemical prop-erties in going down a column in the Periodic Table can be attributed to relativistic effectsin the heavier atoms4.

Therefore, the common approach to building a bonding description of these type com-pounds is to combine the few experimentally known geometric structures with a largernumber of theoretically calculated geometries to infer bonding properties and trends insimple Group 14 compounds. It is, however, first necessary to identify those atomicproperties which distinguish the various Group 14 atoms and which can contribute todifferences in the properties of their corresponding compounds. Of course, the sameproperties which can be used to explain trends in geometric structure could also be usedfor energy properties, such as bond dissociation energies. However, energy propertiestypically involve both an initial state and a final state, where the energetics of the processdepend on the difference in properties between the two states, both involving the sameGroup 14 atom. Trends in energy properties as a function of atom then involve anotherdifferencing step. This can be more subtle and difficult than treating just geometry, whichinvolves only one state. In addition, theoretical methods for calculating geometry are moredeveloped and reliable than for energy difference properties.

1. The nature of the CM bond (M D Ge, Sn, Pb) 3In this review we will first discuss the atomic properties that are expected to be rele-

vant to trends in molecular structure and bonding for compounds of the Group 14 atoms5.Reference will be made mainly to atomic radii6 and atomic orbital energies6 9. The resul-tant conclusions will contribute to interpreting trends in the geometric structures of smallmolecules having the generic formula XH3Y, where X D C, Si, Ge, Sn and Pb, andY is one of the 53 substituents ranging from Y D H to Y D C(O)OCH3. The calcu-lated XH3Y bond energies will also be presented and analyzed. The generated data willallow other derivative thermodynamic quantities for simple generic-type chemical reac-tions involving the Group 14 atom compounds to be calculated. The XH3Y moleculesare restricted to those having a formal single bond between the Group 14 atom X and thedirect bonding atom of the Y group.

II. ATOMIC PROPERTIESThe atomic properties of most relevance to determining the structure and energies ofmolecular compounds have been identified and discussed4,5. The values of these propertiesare collected in Table 16 16. The ground-state electronic configuration of the Group 14atoms is [core]ns2np2, with n D 2,3,4,5 and 6 for C, Si Ge, Sn and Pb, respectively.In LS coupling the electronic ground state has the term symbol 3P . Relativistic effectsare very large for the heaviest atom, lead, with a spin orbit coupling in the thousandsof cm117 . The splitting of the valence np1/2 and np3/2 spinors can affect molecularbinding through their different spatial and energetic interactions with other atoms, even inclosed-shell electronic states18. For simplicity, spin orbit averaged values for calculatedproperties are shown in Table 1 for discussing trends and making comparisons.

The trend in orbital energy values for the valence ns and np atomic orbitals goingdown the Group 14 column is shown in Table 1. The orbital energies are taken from thenumerical atomic Dirac Fock compilation of Desclaux6 and these open-shell systemsdo not rigorously obey Koopmans Theorem19. As such, besides the other approximationsinherent to Koopmans Theorem, these orbital energies can only give a rough measure ofvalues and trends in the atomic orbital ionization energies. In any event, these numbersshow an interesting behavior which must reflect fundamental underlying effects. The(absolute value) np orbital energy is seen to decrease steadily, if not uniformly, withincreasing atom size. There is a relatively very large energy gap between the carbon andsilicon atoms, small gaps among the SiGe and SnPb pairs, and a somewhat largerenergy gap between the Ge and Sn orbital energies. The valence ns atomic orbital energy,on the other hand, is seen to have a sawtooth, alternating behavior in going down theGroup 14 column20. As with the np atomic orbital, there is a very large energy decreasebetween carbon and silicon, but from Si the orbital energies alternately increase anddecrease. Again, the differences between Si and Ge and between Sn and Pb are small,while the gap between Ge and Sn is larger.

The experimental ionization energies7 9 in Table 1 show similar trends; ns ionizationalternates, while np ionization decreases until Pb, where it increases slightly. Again, thereis a large energy gap between carbon and silicon. The calculated atomic radii (hri) forthe Desclaux orbitals6 in Table 1 mirror the general behavior of the orbital and ionizationenergies: sawtooth for ns and uniformly increasing for np, where the np values for Snand Pb are almost equal.

Although it is not completely clear which definition of each property is most appro-priate for discussing molecular bonding (i.e. with or without spin orbit averaging, radialmaxima or expectation values, choice of final state for ionization energy, etc.) the gen-eral trends seem to be roughly independent of definition. The size and energies of thetwo valence atomic orbitals, which properties should be very important for the atoms


TABLE 1. Properties of the Group 14 atoms

Atom C Si Ge Sn Pbn 2 3 4 5 6

Orbital energyans 19.39 14.84 15.52 13.88 15.41npb 11.07 7.57 7.29 6.71 6.48

Ionization energycnsb,d 16.60 13.64 14.43 13.49 16.04npb,e 11.26 8.15 7.90 7.39 7.53

Electron affinityf 1.26 1.39 1.23 1.11 0.36Polarizabilityg 1.76 5.38 6.07 7.7 6.8Electronegativityh

Mullikeni 1.92 1.46 1.40 1.30 1.21Paulingj 2.55 1.90 2.01 1.96 2.33Allenk 2.28 1.76 1.81 1.68 1.91

Atomic radiuslns 1.58 2.20 2.19 2.48 2.39npb 1.74 2.79 2.88 3.22 3.22

a In eV; from Reference 6.b Spin-orbit averaged.c In eV; from References 7 9.d For the process, ns2np2(3P ) ! ns1np2(4P ).e For the process, ns2np2(3P ) ! ns2np1(2P ).f In eV; from References 10 and 11.g In 1024 cm3; from References 12 and 13; dipole polarizability.h Relative to hydrogen D 2.20.i Average of np atomic ionization energy and electron affinity. Data from appropriate lines in this Table. SeeReference 14.j Pauling scale (Reference 1) as calculated in Reference 15.k Weighted average of ns and np ionization energies from the appropriate lines in this Table. See Reference 16.l hri in au; from Reference 6.

chemical behavior, generally show different trends for ns and np. The ns energy alter-nates with increasing atom size while the np energy generally decreases steadily, at leastuntil Pb. The result is a nonuniform trend in energy gap between the ns and np atomicorbitals which can affect the degree of ns np hybridization in chemical bonds involvingthe Group 14 atoms, and, thereby, the chemical behavior of their molecular compounds.On the other hand, the ns np atomic radius (hri) difference increases steadily with atomicnumber, with a particularly large change between carbon and silicon. This difference canalso affect the degree of ns np hybridization through the (radial) overlap which controlsthe bonding effectiveness of resultant hybrid valence orbitals. We can therefore anticipatea somewhat complex, somewhat alternating chemical behavior going down the Group 14column of the Periodic Table1,4,16,20.

Another property which anticipates these trends is the electronegativity, also shown forseveral definitions in Table 1. Paulings empirical electronegativity scale based on bondenergies, as updated by Allerd15, shows a sawtooth behavior, with predictable chemi-cal consequences. Electronegativity is used to correlate a vast number of chemical andphysical properties. Allens revised definition of electronegativity16 as the average config-uration energy of the valence ns and np electrons also shows the alternating behavior withatomic number in the Group 14 column, as expected from the above discussion of orbitaland ionization energies. The Mulliken definition14, based on just the np atomic orbitalionization energy and the corresponding electron affinity, does not show the sawtooth

1. The nature of the CM bond (M D Ge, Sn, Pb) 5behavior, and must be considered deficient for neglecting the effect of the ns atomicorbital on chemical behavior. The Mulliken scale also defines a higher electronegativityfor hydrogen relative to carbon15.

The source of the differential behavior between the ns and np atomic orbitals in goingdown the Group 14 column of the Periodic Table can be attributed to a combinationof screening and relativistic effects, both of which preferentially stabilize the ns atomicorbital4,16. Filling the first transition series affects germanium this way through incompletescreening of its 4s atomic orbital which gives it a higher effective nuclear charge. Fillingthe first lanthanide series analogously stabilizes the Pb 6s atomic orbital through incom-plete screening, which is further enhanced by relativistic effects4,20. Although incompletescreening and relativistic terms also affect the np atomic orbital, the stabilization isstronger for the ns atomic orbital because of its nonzero charge density at the nucleus.

The dipole polarizability term for the atoms (in Table 1) shows the usual gap betweencarbon and silicon, increasing values for Si ! Sn and a decrease at lead. This is anotherreason to expect somewhat unusual behavior for lead compounds compared to the lightermetals.

The role of d-type orbitals is not addressed in Table 1. This subject has been addressedfor second-row atoms in previous reviews21,22 which contain many references to thissubject. It is very difficult to define the energy and radius of the outer-sphere d-typeorbitals (nd) in isolated atoms since they are not occupied in the ground state. Ratherthan make use of some excited state definition, we prefer to postpone a discussion of thissubject until after an inspection of the calculated results on the molecular compounds.

III. CALCULATIONAL METHODSUsing atomic properties alone for predictive capabilities with regard to the geometric andelectronic structure of molecules is often insufficient. Except for weakly bound systems,the chemical bond is more than just a perturbation of the electronic structure of atoms.Molecular properties determined experimentally have been used to infer the electronicstructure description of simple systems, from which predictions are made for more com-plicated molecules using group property and additivity concepts. This empirical approachhas been used very extensively in identifying and defining the determining factors in thegeometric and electronic structure of molecules. These latter are then used in a predictivemode for unknown systems. The opposite approach is to use ab initio quantum chemicalcalculations to determine everything. The disadvantages in the latter methodology is thatno intuitive understanding is derived from the purely mechanical calculational processwhich can be used for chemical systems that are too large for the ab initio machinery.

In this review we will try to combine the best of both approaches. On the one hand,there are very little experimental data for the Group 14 compounds for the atoms belowSi. For simple molecular compounds of Ge, Sn and Pb, ab initio methods can be usedto generate an experimental database from which the electronic structure properties ofsuch compounds can be inferred. Hopefully, the principles learned from this referenceset of molecules can then be applied to larger systems. Although not the subject ofthis chapter, the corresponding carbon and silicon21 systems are also examined to helpelucidate trends in properties going down the complete Group 14 column of the PeriodicTable and for general comparison purposes. More experimental information is available forthe corresponding carbon and silicon compounds so that these can also be used to evaluatethe accuracy of the calculated properties of the germanium, tin and lead database set.

The ab initio methods and approach used here are similar to that reported in previousstudies22 24. The geometries of a generic set of XH3Y molecules were determinedcalculationally. X is any one of the Group 14 atoms (carbon, silicon, germanium, tinand lead) and Y is any of the substituent groups, F, AlH2, BH2, SH, Br, H, CCH, PH2,


NH2, SCH3, Cl, NO, ON, C(O)H, SeCN, NCSe, C(O)F, C(O)NH2, ONO2, NCS, SCN,CH2CH3, C(O)OH, NO2, ONO, PC, CP, NCO, OCN, CN, NC, OCH3, CHDCH2, NNN,OH, CH3, SiH3, GeH3, SnH3, PbH3, CF3, C(O)OCH3, OC(O)CH3, PO, OP, C(O)Cl,OF, OSiH3, C(O)CH3, PO2, OPO, OPO2 and OS(O)OH. The Y substituents are writtenwhere attachment to X is through the leftmost atom. Attachment to X alternately bydifferent atoms of the Y group gives rise to the possibility of linkage isomerism for theY group. The plethora of bonding possibilities with respect to type of atom, attachmentsite, substitution and conformation should combine to give a balanced and comprehensivepicture of the chemical bonding situation in these systems.

The geometries of the XH3Y molecules were optimized at the MP2 (Moeller Plessetto second order) level2 using compact effective potentials (CEP) for the atoms in thefirst two rows of the Periodic Table (BF and AlCl)25 and their relativistic analogs(RCEP) for the main group atoms below the second row26. The RCEP are generated fromDirac Fock all-electron relativistic atomic orbitals6,27 and therefore implicitly include theindirect relativistic effects of the core electrons on the radial distribution of the valenceelectrons18. This could be particularly important for the lead atom. The effective potentialsor pseudopotentials replace the chemically inactive core electrons.

The valence electron Gaussian basis sets were taken from the respective CEP25 andRCEP26 tabulations. The published basis sets show a valence atomic orbital splittingthat can be denoted as (R)CEP-N1G, where N D 3 for first- and second-row atoms,and N D 4 for the heavier main group elements. This type basis set is generically calleddouble-zeta (DZ) for historical reasons connected to Slater orbital (exponential-type) basissets. In these calculations the valence DZ distributions were converted to triple-zeta (TZ)by splitting off the smallest exponent Gaussian member of the contracted (N ) set, to givethe (R)CEP-K 11 valence atomic orbital distribution (K D 2 for first- and second-rowatoms and K D 3 for beyond). The valence TZ Gaussian basis set for each atom wasaugmented by a double (D) set of d-type polarization (DP) functions (all 6 components)taken from the GAMESS tabulation28,29 as follows. The reported29 single Gaussian d-typepolarization function was converted to DP form by scaling the single Gaussian exponent() by 1.4 and 0.4 to form two distinct d-type polarization functions. Both the singleand double set of single Gaussians exponents are displayed in Table 2. The valence TZhydrogen atom basis set was taken from the GAUSSIAN9230 code as the 311G group, andaugmented by a single Gaussian p-type polarization function with exponent 0.9. Overall,this basis set is denoted TZDP. All geometry optimizations were carried out in this basisset at the MP2 level (denoted MP2/TZDP or MP2/CEP-TZDP) using the GAUSSIAN9230set of computer programs.

The extended basis sets are necessary to describe the adaptation of the atom to themolecular environment. Experience has shown31 that the major effect on the radial extentof each atom in a molecule is in the bonding region. A frozen atomic orbital basis set isunable to provide the differential flexibility required in the short, intermediate and long-range radial distances from the nucleus to accurately describe the electron density changesin the molecule. The valence TZ basis set has that flexibility. Analogously, Magnusson32has recently discussed the effect of angular polarization functions on the inner and outerparts of the valence atomic orbitals of the main group elements The different polarizationneeds in the different regions of space about each atom in the molecule leads to the useof a double set of d-type basis function.

The MP2 level calculation is the first step beyond the Hartree Fock (HF) level33,34,and is thereby defined as a post-Hartree Fock method. Theory predicts35 and actual cal-culations have shown2 that HF level calculated geometries generally give bond distancesthat are too short compared to experiment for normal covalent bonds. For these cases,MP2 level optimized geometries give better agreement with experiment36. The same is

1. The nature of the CM bond (M D Ge, Sn, Pb) 7TABLE 2. Polarization and diffuse Gaussian exponentsa

Polarization

single doubleb Diffusesingle

Atom 1 2 GaussianH 0.9000 0.03237B 0.7000 0.9800 0.2800 0.02559C 0.7500 1.050 0.3000 0.03691N 0.8000 1.120 0.3200 0.05171O 0.8500 1.190 0.3400 0.06181F 0.9000 1.260 0.3600 0.07461Al 0.3250 0.4550 0.1300 0.01691Si 0.3950 0.5530 0.1580 0.02324P 0.4650 0.6510 0.1860 0.02919S 0.5420 0.7588 0.2168 0.03461Cl 0.6000 0.8400 0.2400 0.04395Ge 0.2460 0.3444 0.0984 0.02132Se 0.3200 0.4480 0.1280 0.02934Br 0.3600 0.5040 0.1440 0.03574Sn 0.1830 0.2562 0.0732 0.01858Pb 0.1640 0.2296 0.0656 0.01574a Except for H, the polarization functions are d-type and the diffuse functionsare sp-type. For the hydrogen atom polarization is p-type and diffuse is s-type.b 1 D 1.4; 2 D 0.4; values of are from Ref. 29.

true for vibrational frequencies37. The reason for the improved description of the normalcovalent bond at the post-HF level is the improved description of the incipient homolyticbond dissociation process (i.e. reduced ionicity) at the MP2 level compared to HF in theneighborhood of the equilibrium bond distances. The resultant geometry optimized bondlengths are listed in Tables 3 8.

TABLE 3. Bond distances (in A) not involving Group 14 atomsaBond type

BHb NHb OH NDN NN NO NDOCompound AlHb PHb SH PO PDOCH3NO2 1.241bSiH3NO2 1.252bGeH3NO2 1.250bSnH3NO2 1.251bPbH3NO2 1.248bCH3ONO 1.411 1.203SiH3ONO 1.481 1.180GeH3ONO 1.374 1.216SnH3ONO 1.338 1.231PbH3ONO 1.306 1.245CH3OH 0.967SiH3OH 0.965GeH3OH 0.968SnH3OH 0.968PbH3OH 0.971CH3NNN 1.246 1.159SiH3NNN 1.233 1.168

(continued overleaf )


TABLE 3. (continued )Bond type

BHb NHb OH NDN NN NO NDOCompound AlHb PHb SH PO PDOGeH3NNN 1.237 1.169SnH3NNN 1.234 1.173PbH3NNN 1.242 1.175CH3ONO2 1.422 1.217

1.223bSiH3ONO2 1.405 1.214

1.232bGeH3ONO2 1.388 1.218

1.236bSnH3ONO2 1.366 1.220

1.247bPbH3ONO2 1.345 1.223

1.259bCH3NO 1.233SiH3NO 1.252GeH3NO 1.240SnH3NO 1.238PbH3NO 1.224CH3ON 1.251SiH3ONcGeH3ON 1.277SnH3ON 1.285PbH3ON 1.257CH3SH 1.320SiH3SH 1.322GeH3SH 1.322SnH3SH 1.322PbH3SH 1.321CH3C(O)OH 0.976SiH3C(O)OH 0.980GeH3C(O)OH 0.980SnH3C(O)OH 0.981PbH3C(O)OH 0.981CH3NH2 1.019SiH3NH2 1.014GeH3NH2 1.018SnH3NH2 1.019PbH3NH2 1.023CH3PH2 1.412SiH3PH2 1.413GeH3PH2 1.413SnH3PH2 1.414PbH3PH2 1.413CH3BH2 1.193SiH3BH2 1.190GeH3BH2 1.189SnH3BH2 1.189PbH3BH2 1.186CH3AlH2 1.584SiH3AlH2 1.582GeH3AlH2 1.581SnH3AlH2 1.582PbH3AlH2 1.579CH3C(O)NH2 1.011

1. The nature of the CM bond (M D Ge, Sn, Pb) 9TABLE 3. (continued )

Bond type

BHb NHb OH NDN NN NO NDOCompound AlHb PHb SH PO PDOSiH3C(O)NH2 1.012GeH3C(O)NH2 1.012SnH3C(O)NH2 1.013PbH3C(O)NH2 1.013CH3PO 1.513SiH3PO 1.527GeH3PO 1.524SnH3PO 1.524PbH3PO 1.520CH3OP 1.621SiH3OP 1.640GeH3OP 1.631SnH3OP 1.631PbH3OP 1.624CH3PO2 1.483bSiH3PO2 1.488bGeH3PO2 1.489bSnH3PO2 1.491bPbH3PO2 1.491bCH3OPO 1.627 1.499SiH3OPO 1.627 1.499GeH3OPO 1.615 1.503SnH3OPO 1.602 1.509PbH3OPO 1.582 1.523CH3OF 1.455dSiH3OF 1.465dGeH3OF 1.464dSnH3OF 1.470dPbH3OF 1.473dCH3OS(O)OH 0.979 1.630e 1.659f 1.464gSiH3OS(O)OH 0.980 1.633e 1.641f 1.465gGeH3OS(O)OH 0.980 1.611e 1.652f 1.470gSnH3OS(O)OH 0.980 1.590e 1.649f 1.482gPbH3OS(O)OH 0.979 1.564e 1.651f 1.500gCH3OPO2 1.592 1.476

1.482hSiH3OPO2 1.586 1.475

1.484hGeH3OPO2 1.580 1.477

1.487hSnH3OPO2 1.572 1.478

1.492hPbH3OPO2 1.563 1.478

1.501h

a MP2 optimized geometries in the TZDP basis set.b Averaged.c Not calculated.d OF.e (X) OS.f SO(H).g SDO.h Facing X.


TABLE 4. Bond distances (in A) involving carbona

Bond type

CHb CC CDCc CN CDNc CO CDOc CF CBCP CDPc CS CDSc CCl CAl

Compound CSe CDSec CBrCH3OCH3 1.095 1.423SiH3OCH3 1.093 1.434GeH3OCH3 1.094 1.433SnH3OCH3 1.095 1.430PbH3OCH3 1.097 1.432CH3NO2 1.087 1.496CH3ONO 1.090 1.446CH3OH 1.093 1.433CH3Cl 1.086 1.796CH3CP 1.093 1.471 1.571SiH3CP 1.577GeH3CP 1.577SnH3CP 1.578PbH3CP 1.578CH3PC 1.090 1.859 1.639SiH3PC 1.636GeH3PC 1.635SnH3PC 1.633PbH3PC 1.633CH3CH3 1.092 1.533SiH3CH3 1.092GeH3CH3 1.091SnH3CH3 1.091PbH3CH3 1.088CH4 1.089CH3CHCH2 1.093 1.503 1.339

1.088d1.085e

SiH3CHCH2 1.089d 1.3461.086e

GeH3CHCH2 1.088d 1.3431.086e

SnH3CHCH2 1.089d 1.3451.087e

PbH3CHCH2 1.086d 1.3411.087e

CH3NNN 1.090 1.487CH3CN 1.090 1.466 1.174SiH3CN 1.178GeH3CN 1.178SnH3CN 1.179PbH3CN 1.180CH3NC 1.089 1.432 1.185SiH3NC 1.189GeH3NC 1.189SnH3NC 1.190PbH3NC 1.190CH3SCN 1.089 1.181 1.812 1.684SiH3SCN 1.181 1.685


Bond type


Compound CSe CDSec CBrGeH3SCN 1.182 1.683SnH3SCN 1.183 1.682PbH3SCN 1.184 1.680CH3NCS 1.091 1.444 1.204 1.571SiH3NCS 1.204 1.566GeH3NCS 1.208 1.569SnH3NCS 1.202 1.574PbH3NCS 1.218 1.574CH3OCN 1.089 1.180 1.465 1.303SiH3OCN 1.180 1.299GeH3OCN 1.182 1.296SnH3OCN 1.183 1.292PbH3OCN 1.185 1.291CH3NCO 1.090 1.457 1.216 1.186SiH3NCO 1.213 1.183GeH3NCO 1.217 1.185SnH3NCO 1.213 1.188PbH3NCO 1.226 1.189CH3SCH3 1.091 1.795SiH3SCH3 1.090 1.817GeH3SCH3 1.090 1.815SnH3SCH3 1.089 1.819PbH3SCH3 1.090 1.817CH3CH2CH3 1.093 1.531

1.095e 1.531SiH3CH2CH3 1.095e 1.540

1.093GeH3CH2CH3 1.095e 1.536

1.094SnH3CH2CH3 1.094 1.537PbH3CH2CH3 1.091e 1.531

1.094CH3CF3 1.089 1.503 1.355SiH3CF3 1.361GeH3CF3 1.361SnH3CF3 1.364PbH3CF3 1.359CH3CCH 1.092 1.467

1.063d 1.217SiH3CCH 1.066 1.225GeH3CCH 1.065 1.224SnH3CCH 1.066 1.226PbH3CCH 1.066 1.225CH3ONO2 1.089 1.446CH3F 1.090 1.400CH3NO 1.092 1.484CH3ON 1.088 1.500CH3C(O)H 1.092 1.507 1.221





Compound CSe CDSec CBr1.109d

SiH3C(O)H 1.114 1.231GeH3C(O)H 1.114 1.226SnH3C(O)H 1.115 1.227PbH3C(O)H 1.112 1.221CH3Br 1.086 1.944CH3SeCN 1.088 1.181 1.961 1.849SiH3SeCN 1.182 1.851GeH3SeCN 1.182 1.849SnH3SeCN 1.182 1.850PbH3SeCN 1.183 1.847CH3NCSe 1.091 1.440 1.201 1.736SiH3NCSe 1.202 1.718GeH3NCSe 1.199 1.725SnH3NCSe 1.199 1.729PbH3NCSe 1.197 1.735CH3SH 1.088 1.806CH3C(O)OH 1.090 1.506 1.368 1.216SiH3C(O)OH 1.369 1.220GeH3C(O)OH 1.370 1.217SnH3C(O)OH 1.374 1.217PbH3C(O)OH 1.369 1.213CH3C(O)F 1.090 1.498 1.194 1.378SiH3C(O)F 1.195 1.397GeH3C(O)F 1.194 1.395SnH3C(O)F 1.194 1.405PbH3C(O)F 1.190 1.401CH3NH2 1.093 1.477CH3PH2 1.091 1.862CH3BH2 1.095 1.562CH3AlH2 1.094 1.963CH3C(O)NH2 1.091 1.519 1.381 1.227SiH3C(O)NH2 1.374 1.236GeH3C(O)NH2 1.374 1.231SnH3C(O)NH2 1.375 1.231PbH3C(O)NH2 1.371 1.225CH3C(O)OCH3 1.090 1.509 1.361 1.218

1.089 1.448fSiH3C(O)OCH3 1.088 1.363 1.223

1.454fGeH3C(O)OCH3 1.088 1.365 1.219

1.454fSnH3C(O)OCH3 1.088 1.369 1.219

1.455fPbH3C(O)OCH3 1.088 1.363 1.214

1.458fSiH3OC(O)CH3 1.090 1.505 1.363 1.220GeH3OC(O)CH3 1.090 1.508 1.351 1.225SnH3OC(O)CH3 1.090 1.507 1.333 1.236


Bond type


Compound CSe CDSec CBrPbH3OC(O)CH3 1.090 1.508 1.314 1.249CH3PO 1.094 1.848CH3OP 1.090 1.459CH3C(O)Cl 1.090 1.502 1.195 1.823SiH3C(O)Cl 1.192 1.875GeH3C(O)Cl 1.188 1.903SnH3C(O)Cl 1.188 1.903PbH3C(O)Cl 1.187 1.885CH3C(O)CH3 1.092 1.518b 1.226SiH3C(O)CH3 1.094 1.515 1.234GeH3C(O)CH3 1.093 1.517 1.228SnH3C(O)CH3 1.094 1.517 1.227PbH3C(O)CH3 1.093 1.510 1.220CH3PO2 1.089 1.811CH3OPO 1.089 1.457CH3OF 1.092 1.423CH3OS(O)OH 1.089 1.453CH3OS(O)OH 1.087 1.465a MP2 optimized geometries in the TZDP basis set.b Average bond lengths.c Double or triple bond.d CH group.e CH2 group.f OCH3.

TABLE 5. Bond distances (in A) involving silicona

Bond type

SiHb SiC SiN SiO SiF SiBSiSi SiP SiS SiCl SiAlSiGe SiSe SiBrSiSn

Compound SiPbSiH3OCH3 1.475 1.660SiH3NO2 1.465 1.847SiH3ONO 1.471 1.705SiH3OH 1.473 1.665SiH3Cl 1.468 2.070SiH3CP 1.473 1.853SiH3PC 1.468 2.279SiH3CH3 1.477 1.879SiH3SiH3 1.475 2.347SiH3GeH3 1.474 2.389SiH3SnH3 1.475 2.579SiH3PbH3 1.473 2.584SiH4 1.472




SiHb SiC SiN SiO SiF SiBSiSi SiP SiS SiCl SiAlSiGe SiSe SiBrSiSn

Compound SiPbSiH3CHCH2 1.476 1.868SiH3NNN 1.471 1.763SiH3CN 1.468 1.860SiH3NC 1.467 1.768SiH3SCN 1.468 2.165SiH3NCS 1.470 1.738SiH3OCN 1.466 1.715SiH3NCO 1.470 1.736SiH3SCH3 1.474 2.116SiH3CH2CH3 1.477 1.882SiH3CF3 1.469 1.929SiH3CCH 1.472 1.838SiH3ONO2 1.467 1.729SiH3F 1.469 1.619SiH3NO 1.471 1.853SiH3ONcSiH3C(O)H 1.473 1.923SiH3Br 1.467 2.234SiH3SeCN 1.468 2.320SiH3NCSe 1.470 1.751SiH3SH 1.471 2.129SiH3C(O)OH 1.470 1.922SiH3C(O)F 1.468 1.921SiH3PH2 1.474 2.266SiH3NH2 1.477 1.739SiH3BH2 1.478 2.022SiH3AlH2 1.479 2.486SiH3C(O)NH2 1.473 1.922SiH3C(O)OCH3 1.471 1.920SiH3OC(O)CH3 1.469 1.710SiH3PO 1.476 2.356SiH3OP 1.469 1.715SiH3C(O)Cl 1.468 1.920SiH3C(O)CH3 1.474 1.933SiH3PO2 1.467 2.285SiH3OPO 1.468 1.707SiH3OF 1.469 1.709SiH3OSiH3 1.474 1.656GeH3OSiH3 1.476 1.654SnH3OSiH3 1.478 1.648PbH3OSiH3 1.480 1.650SiH3OS(O)OH 1.469 1.707SiH3OPO2 1.466 1.716a MP2 optimized geometries in the TZDP basis set.b Average bond lengths.c Not calculated.

1. The nature of the CM bond (M D Ge, Sn, Pb) 15TABLE 6. Bond distances (in A) involving germaniuma

Bond type

GeHb GeC GeN GeO GeF GeBGeSi GeP GeS GeCl GeAlGeGe GeSe GeBrGeSn

Compound GePbGeH3OCH3 1.521 1.779GeH3NO2 1.510 1.944GeH3ONO 1.514 1.860GeH3OH 1.519 1.783GeH3Cl 1.513 2.171GeH3CP 1.518 1.930GeH3PC 1.513 2.363GeH3CH3 1.524 1.955GeH3SiH3 1.522 2.389GeH3GeH3 1.522 2.427GeH3SnH3 1.522 2.610GeH3PbH3 1.520 2.621GeH4 1.518GeH3CHCH2 1.522 1.943GeH3NNN 1.515 1.876GeH3CN 1.511 1.937GeH3NC 1.510 1.861GeH3SCN 1.513 2.259GeH3NCS 1.513 1.847GeH3OCN 1.510 1.841GeH3NCO 1.515 1.844GeH3SCH3 1.520 2.206GeH3CH2CH3 1.525 1.961GeH3CF3 1.514 2.000GeH3CCH 1.517 1.913GeH3ONO2 1.511 1.851GeH3F 1.514 1.738GeH3NO 1.519 1.972GeH3ON 1.512 1.897GeH3C(O)H 1.520 2.000GeH3Br 1.513 2.321GeH3SeCN 1.514 2.398GeH3NCSe 1.513 1.846GeH3SH 1.517 2.221GeH3C(O)OH 1.516 1.994GeH3C(O)F 1.513 1.992GeH3NH2 1.522 1.848GeH3PH2 1.521 2.333GeH3BH2 1.525 2.072GeH3AlH2 1.528 2.504GeH3C(O)NH2 1.520 1.997GeH3C(O)OCH3 1.517 1.993GeH3OC(O)CH3 1.513 1.834GeH3PO 1.524 2.418GeH3OP 1.514 1.840GeH3C(O)Cl 1.513 1.998GeH3C(O)CH3 1.521 2.011GeH3PO2 1.513 2.348




GeHb GeC GeN GeO GeF GeBGeSi GeP GeS GeCl GeAlGeGe GeSe GeBrGeSn

Compound GePbGeH3OPO 1.512 1.838GeH3OF 1.515 1.822GeH3OSiH3 1.518 1.779GeH3OS(O)OH 1.512 1.838GeH3OPO2 1.510 1.848a MP2 optimized geometries in the CEP-TZDP basis set.b Average bond lengths.

TABLE 7. Bond distances (in A) involving tina

Bond type

SnHb SnC SnN SnO SnF SnBSnSi SnP SnS SnCl SnAlSnGe SnSe SnBrSnSn

Compound SnPbSnH3OCH3 1.691 1.959SnH3NO2 1.680 2.131SnH3ONO 1.683 2.076SnH3OH 1.689 1.963SnH3Cl 1.682 2.350SnH3CP 1.688 2.110SnH3PC 1.682 2.545SnH3CH3 1.695 2.140SnH3SiH3 1.693 2.579SnH3GeH3 1.693 2.610SnH3SnH3 1.693 2.785SnH3PbH3 1.692 2.797SnH4 1.689SnH3CHCH2 1.692 2.126SnH3NNN 1.684 2.056SnH3CN 1.681 2.117SnH3NC 1.680 2.039SnH3SCN 1.681 2.448SnH3NCS 1.682 2.017SnH3OCN 1.679 2.023SnH3NCO 1.684 2.015SnH3SCH3 1.690 2.389SnH3CH2CH3 1.696 2.148SnH3CF3 1.684 2.192SnH3CCH 1.687 2.088SnH3ONO2 1.680 2.051SnH3F 1.684 1.910SnH3NO 1.690 2.189SnH3ON 1.682 2.077SnH3C(O)H 1.690 2.197SnH3Br 1.684 2.496


Bond type

SnHb SnC SnN SnO SnF SnBSnSi SnP SnS SnCl SnAlSnGe SnSe SnBrSnSn

Compound SnPbSnH3SeCN 1.683 2.584SnH3NCSe 1.682 2.024SnH3SH 1.687 2.402SnH3C(O)OH 1.686 2.182SnH3C(O)F 1.683 2.178SnH3NH2 1.692 2.031SnH3PH2 1.691 2.521SnH3BH2 1.696 2.264SnH3AlH2 1.698 2.696SnH3C(O)NH2 1.691 2.186SnH3C(O)OCH3 1.687 2.180SnH3OC(O)CH3 1.684 2.039SnH3PO 1.694 2.629SnH3OP 1.684 2.028SnH3C(O)Cl 1.683 2.189SnH3C(O)CH3 1.692 2.210SnH3PO2 1.682 2.540SnH3OPO 1.681 2.040SnH3OF 1.684 2.010SnH3OSiH3 1.687 1.959SnH3OS(O)OH 1.682 2.042SnH3OPO2 1.679 2.042a MP2 optimized geometries in the TZDP basis set.b Average bond lengths.

TABLE 8. Bond distances (in A) involving leada

Bond type

PbHb PbC PbN PbO PbF PbBPbSi PbP PbS PbCl PbAlPbGe PbSe PbBrPbSn

Compound PbPbPbH3OCH3 1.735 2.064PbH3NO2 1.724 2.180PbH3ONO 1.726 2.206PbH3OH 1.733 2.070PbH3Cl 1.726 2.414PbH3CP 1.732 2.169PbH3PC 1.726 2.598PbH3CH3 1.742 2.181PbH3SiH3 1.743 2.584PbH3GeH3 1.743 2.621PbH3SnH3 1.744 2.797PbH3PbH3 1.742 2.812PbH4 1.735




PbHb PbC PbN PbO PbF PbBPbSi PbP PbS PbCl PbAlPbGe PbSe PbBrPbSn

Compound PbPbPbH3CHCH2 1.742 2.167PbH3NNN 1.728 2.157PbH3CN 1.724 2.180PbH3NC 1.721 2.130PbH3SCN 1.726 2.497PbH3NCS 1.725 2.139PbH3OCN 1.721 2.134PbH3NCO 1.726 2.126PbH3SCH3 1.737 2.433PbH3CH2CH3 1.746 2.182PbH3CF3 1.730 2.206PbH3CCH 1.730 2.144PbH3ONO2 1.726 2.168PbH3F 1.726 2.026PbH3NO 1.744 2.264PbH3ON 1.732 2.194PbH3C(O)H 1.739 2.231PbH3Br 1.728 2.549PbH3SeCN 1.728 2.624PbH3NCSe 1.724 2.117PbH3SH 1.733 2.451PbH3C(O)OH 1.733 2.210PbH3C(O)F 1.728 2.212PbH3NH2 1.738 2.123PbH3PH2 1.741 2.546PbH3BH2 1.745 2.279PbH3AlH2 1.750 2.696PbH3C(O)NH2 1.740 2.216PbH3C(O)OCH3 1.735 2.208PbH3OC(O)CH3 1.732 2.174PbH3PO 1.747 2.639PbH3OP 1.728 2.131PbH3C(O)Cl 1.728 2.230PbH3C(O)CH3 1.743 2.238PbH3PO2 1.727 2.563PbH3OPO 1.728 2.194PbH3OF 1.728 2.100PbH3OSiH3 1.730 2.075PbH3OS(O)OH 1.729 2.184PbH3OPO2 1.723 2.179a MP2 optimized geometries in the TZDP basis set.b Average bond lengths.

The MP2/TZDP optimized structures were then used to calculate the stationary stategeometry force constants and harmonic vibrational frequencies, also at the MP2 level.These results serve several purposes. Firstly, they test that the calculated geometry isreally an energy minimum by showing all real frequencies in the normal coordinateanalysis. Secondly, they provide values of the zero-point energy (ZPE) that can be used

1. The nature of the CM bond (M D Ge, Sn, Pb) 19to convert the total electronic energy differences to thermodynamic enthalpies that takeinto account zero-point vibrational energy differences in chemical reactions. Thirdly, theyprovide values of vibrational frequencies in the XH3Y series that can be compared for atomand substituent effects. This information contributes another dimension to the analysis ofthe electronic structure description of the bonding in these systems.

Another property obtained at the MP2 level using the relaxed MP2 densities calculatedas energy derivatives38,39 are the Mulliken populations and atomic charges. A compre-hensive discussion of the whole topic of population analyses has recently been given40.The specific deficiencies of the Mulliken partitioning of the basis function space in thewave function charge distribution is well known41. Clearly, great care must be taken ininterpreting trends in structure properties based on derived atomic charges alone. Theindividual MP2 atomic charges were summed to calculate group charges for all the XH3and Y substituents. These are shown in Table 9. The individual s, p and (five compo-nent) d contributions to the atomic populations at the MP2 level for the X atoms in allthe XH3Y molecules are found in Table 10. The individual atomic charges for all theatoms in XH3Y are tabulated in Tables 11 15. The MP2/TZDP level dipole moments aretabulated in Table 16.

TABLE 9. Mulliken charges on the H and XH3 groups in RYa

YnR H CH3 SiH3 GeH3 SnH3 PbH3F 0.412 0.327 0.649 0.622 0.736 0.669AlH2 0.080 0.221 0.065 0.174 0.235 0.193BH2 0.027 0.171 0.141 0.131 0.132 0.136SH 0.165 0.036 0.319 0.350 0.398 0.455Br 0.139 0.050 0.161 0.267 0.368 0.452H 0. 0.147 0.075 0.060 0.089 0.101CCH 0.191 0.071 0.447 0.332 0.457 0.444PH2 0.051 0.126 0.137 0.171 0.207 0.243NH2 0.257 0.094 0.358 0.342 0.466 0.420SCH3 0.138 0.003 0.288 0.312 0.374 0.417Cl 0.211 0.066 0.357 0.388 0.464 0.524NO 0.226 0.133 0.394 0.333 0.391 0.318ON 0.319 0.174 b 0.493 0.587 0.493C(O)H 0.098 0.049 0.277 0.229 0.279 0.274SeCN 0.104 0.057 0.141 0.240 0.391 0.454NCSe 0.304 0.235 0.549 0.474 0.587 0.563C(O)F 0.130 0.091 0.336 0.281 0.344 0.355C(O)NH2 0.079 0.013 0.244 0.181 0.235 0.217ONO2 0.306 0.139 0.496 0.494 0.593 0.584NCS 0.302 0.218 0.511 0.482 0.597 0.594SCN 0.187 0.086 0.391 0.434 0.500 0.564CH2CH3 0.138 0.140 0.256 0.234 0.310 0.294C(O)OH 0.115 0.059 0.311 0.254 0.307 0.311NO2 0.267 0.188 0.478 0.445 0.535 0.526ONO 0.267 0.111 0.425 0.430 0.506 0.484PC 0.145 0.037 0.365 0.379 0.383 0.445CP 0.183 0.087 0.387 0.317 0.381 0.409NCO 0.299 0.194 0.494 0.465 0.600 0.568OCN 0.364 0.234 0.604 0.615 0.715 0.696CN 0.266 0.241 0.512 0.465 0.506 0.528NC 0.334 0.309 0.553 0.502 0.605 0.579OCH3 0.289 0.080 0.408 0.421 0.566 0.499



TABLE 9. (continued )YnR H CH3 SiH3 GeH3 SnH3 PbH3

CHCH2 0.125 0.007 0.294 0.248 0.318 0.333NNN 0.288 0.171 0.445 0.435 0.553 0.547OH 0.303 0.070 0.388 0.379 0.526 0.468CH3 0.147 0. 0.273 0.260 0.330 0.329SiH3 0.075 0.273 0. 0.068 0.139 0.129GeH3 0.060 0.260 0.068 0. 0.128 0.094SnH3 0.089 0.330 0.139 0.128 0. 0.089PbH3 0.101 0.329 0.129 0.094 0.089 0.CF3 0.103 0.085 0.285 0.222 0.283 0.288C(O)OCH3 0.117 0.051 0.312 0.243 0.360 0.376OC(O)CH3 0.307 0.138 0.479 0.575 0.686 0.640PO 0.034 0.117 0.083 0.088 0.124 0.106OP 0.355 0.171 0.496 0.497 0.622 0.587C(O)Cl 0.153 0.103 0.363 0.311 0.384 0.407C(O)CH3 0.079 0.016 0.231 0.166 0.215 0.200PO2 0.065 0.043 0.248 0.265 0.305 0.324OPO 0.325 0.149 0.479 0.479 0.583 0.555OF 0.319 0.126 0.480 0.476 0.595 0.570OSiH3 0.388 0.110 0.430 0.455 0.626 0.582OS(O)OH 0.347 0.147 0.480 0.484 0.588 0.575OPO2 0.359 0.199 0.544 0.564 0.683 0.687a All results are at the geometry optimized MP2/TZDP level. Connectivity is to the leftmost atom in Y.b Not calculated.

TABLE 10. MP2/TZDP Mulliken atomic orbital populations for X in XH3Ya

C Si Ge Sn Pb

X D Y s p d s p d s p d s p d s p dF 1.23 2.71 0.12 1.07 1.79 0.32 1.20 1.85 0.22 1.16 1.75 0.19 1.32 1.70 0.12H 1.20 3.23 0.06 1.16 2.26 0.23 1.28 2.34 0.16 1.23 2.25 0.16 1.35 2.16 0.10Cl 1.23 3.01 0.11 1.14 2.00 0.31 1.26 2.03 0.21 1.22 1.94 0.19 1.35 1.84 0.11Br 1.25 3.14 0.11 1.21 2.12 0.32 1.31 2.12 0.21 1.25 2.02 0.19 1.38 1.92 0.10OH 1.25 2.84 0.12 1.08 1.89 0.33 1.20 1.95 0.23 1.15 1.83 0.20 1.31 1.79 0.12SH 1.21 3.09 0.10 1.17 2.10 0.30 1.29 2.16 0.21 1.23 2.06 0.20 1.36 1.97 0.11NH2 1.24 2.95 0.10 1.11 2.01 0.31 1.21 2.06 0.21 1.16 1.93 0.19 1.31 1.88 0.10PH2 1.22 3.24 0.08 1.17 2.21 0.25 1.27 2.24 0.18 1.22 2.14 0.17 1.35 2.04 0.08BH2 1.19 3.25 0.07 1.13 2.28 0.21 1.26 2.33 0.14 1.21 2.25 0.14 1.34 2.17 0.06AlH2 1.17 3.41 0.06 1.14 2.40 0.19 1.20 2.39 0.13 1.16 2.29 0.13 1.31 2.12 0.06CH3 1.18 3.06 0.06 1.14 2.11 0.26 1.25 2.16 0.17 1.19 2.06 0.16 1.32 1.98 0.08SiH3 1.22 3.36 0.06 1.18 2.38 0.22 1.27 2.38 0.15 1.21 2.27 0.15 1.36 2.15 0.08GeH3 1.22 3.37 0.07 1.22 2.42 0.22 1.31 2.42 0.15 1.23 2.32 0.16 1.40 2.17 0.08SnH3 1.25 3.43 0.06 1.22 2.50 0.22 1.30 2.52 0.14 1.23 2.41 0.15 1.42 2.26 0.08PbH3 1.27 3.42 0.06 1.24 2.51 0.22 1.30 2.55 0.15 1.23 2.44 0.15 1.41 2.30 0.08CN 1.17 3.08 0.08 1.14 2.10 0.25 1.25 2.14 0.17 1.19 2.02 0.15 1.33 1.94 0.08NC 1.32 2.92 0.10 1.15 1.97 0.28 1.23 1.99 0.18 1.18 1.87 0.15 1.33 1.83 0.09NO 1.26 2.98 0.08 1.17 2.02 0.25 1.29 2.07 0.17 1.25 1.99 0.16 1.40 1.93 0.10ON 1.27 2.85 0.07 1.29 1.94 0.20 1.23 1.84 0.20 1.41 1.81 0.12PO 1.20 3.29 0.07 1.19 2.30 0.22 1.31 2.34 0.15 1.26 2.23 0.15 1.41 2.12 0.09OP 1.26 2.84 0.10 1.10 1.88 0.31 1.24 1.92 0.22 1.20 1.82 0.20 1.37 1.76 0.12CP 1.13 3.06 0.10 1.18 2.11 0.27 1.28 2.16 0.18 1.21 2.04 0.15 1.33 1.96 0.07PC 1.21 3.20 0.08 1.18 2.16 0.26 1.28 2.17 0.17 1.23 2.06 0.17 1.38 1.97 0.09OF 1.25 2.82 0.11 1.11 1.87 0.30 1.24 1.92 0.21 1.19 1.82 0.19 1.34 1.75 0.12

1. The nature of the CM bond (M D Ge, Sn, Pb) 21TABLE 10. (continued )X D C Si Ge Sn PbY s p d s p d s p d s p d s p d

CCH 1.24 3.06 0.09 1.21 2.10 0.27 1.32 2.15 0.18 1.26 2.03 0.16 1.35 1.93 0.08C(O)H 1.15 3.11 0.07 1.20 2.17 0.24 1.31 2.23 0.17 1.24 2.12 0.16 1.37 2.04 0.09CHCH2 1.19 3.09 0.08 1.18 2.13 0.26 1.28 2.20 0.18 1.21 2.10 0.17 1.33 2.01 0.09OCH3 1.25 2.85 0.12 1.08 1.89 0.33 1.21 1.93 0.22 1.16 1.82 0.19 1.33 1.78 0.10SCH3 1.21 3.12 0.10 1.17 2.11 0.30 1.29 2.17 0.21 1.23 2.08 0.21 1.37 1.98 0.11OSiH3 1.26 2.86 0.12 1.09 1.90 0.34 1.20 1.94 0.23 1.15 1.82 0.19 1.33 1.79 0.11CH2CH3 1.19 3.09 0.09 1.14 2.12 0.26 1.25 2.18 0.17 1.19 2.09 0.16 1.33 2.00 0.08OCN 1.27 2.84 0.11 1.12 1.88 0.29 1.25 1.91 0.19 1.21 1.82 0.16 1.37 1.77 0.09NCO 1.28 2.92 0.10 1.13 1.96 0.30 1.22 1.99 0.20 1.17 1.85 0.17 1.33 1.82 0.09SCN 1.22 3.10 0.09 1.19 2.09 0.29 1.30 2.15 0.20 1.25 2.05 0.20 1.39 1.95 0.11NCS 1.31 2.91 0.10 1.15 1.96 0.30 1.23 1.98 0.19 1.17 1.84 0.15 1.34 1.83 0.09SeCN 1.24 3.22 0.10 1.23 2.20 0.29 1.32 2.20 0.20 1.25 2.10 0.18 1.39 1.98 0.09NCSE 1.31 2.91 0.10 1.13 1.97 0.29 1.21 1.97 0.17 1.16 1.86 0.13 1.31 1.82 0.07NNN 1.25 2.94 0.10 1.14 1.99 0.31 1.25 2.03 0.21 1.20 1.92 0.19 1.36 1.86 0.11ONO 1.25 2.89 0.11 1.12 1.92 0.30 1.25 1.99 0.20 1.21 1.91 0.18 1.35 1.84 0.11NO2 1.29 2.97 0.08 1.17 2.02 0.27 1.27 2.06 0.20 1.22 1.95 0.18 1.36 1.88 0.12OPO 1.26 2.86 0.11 1.10 1.91 0.30 1.23 1.96 0.21 1.19 1.87 0.20 1.36 1.78 0.13PO2 1.22 3.26 0.07 1.21 2.26 0.24 1.33 2.30 0.17 1.27 2.20 0.18 1.39 2.11 0.11C(O)F 1.18 3.12 0.07 1.19 2.16 0.24 1.29 2.23 0.18 1.23 2.12 0.17 1.35 2.04 0.10C(O)Cl 1.18 3.10 0.07 1.20 2.14 0.25 1.30 2.19 0.18 1.24 2.08 0.18 1.36 2.00 0.10C(O)OH 1.19 2.12 0.07 1.19 2.16 0.24 1.29 2.21 0.17 1.23 2.11 0.17 1.35 2.03 0.10C(O)NH2 1.20 3.14 0.06 1.20 2.18 0.24 1.30 2.24 0.18 1.24 2.15 0.18 1.36 2.07 0.11C(O)CH3 1.17 3.14 0.07 1.20 2.19 0.24 1.32 2.25 0.17 1.26 2.17 0.17 1.38 2.09 0.09CF3 1.20 3.12 0.07 1.20 2.18 0.25 1.30 2.26 0.18 1.24 2.16 0.18 1.36 2.10 0.11ONO2 1.26 2.86 0.11 1.11 1.89 0.30 1.24 1.93 0.21 1.20 1.84 0.19 1.35 1.76 0.12OPO2 1.26 2.84 0.11 1.11 1.88 0.30 1.23 1.92 0.20 1.20 1.84 0.19 1.36 1.74 0.12C(O)OCH3 1.20 3.11 0.07 1.20 2.15 0.24 1.30 2.21 0.17 1.24 2.11 0.17 1.35 1.96 0.09OC(O)CH3 1.26 2.87 0.11 1.10 1.90 0.30 1.23 1.94 0.21 1.19 1.86 0.20 1.34 1.78 0.12OS(O)OH 1.26 2.89 0.11 1.09 1.91 0.31 1.23 1.95 0.22 1.19 1.86 0.20 1.34 1.77 0.13a Geometry optimized at the MP2/TZDP level, 5 d-type distribution. Connectivity is to the leftmost atom in Y.

TABLE 11. Mulliken atomic charges calculated at the MP2 level for carbon compoundsa

Atom type

H(C)b B C N O F H (A)Al P S Cl

Compound Se Br

CH3OCH3 0.128 0.305 0.161CH3NO2 0.180 0.353 0.479 0.143

0.148CH3ONO 0.156 0.358 0.407 0.045

0.250cCH3OH 0.128 0.314 0.359 0.289 (O)CH3Cl 0.171 0.448 0.066CH3CP 0.181 0.456 0.168CH3PC 0.198 0.556f 0.523

0.559CH3CH3 0.138 0.415CH4 0.147 0.590



TABLE 11. (continued )Atom type


Compound Se Br

CH3CHCH2 0.149f 0.440f0.109 0.0760.119g 0.278g

CH3NNN 0.160 0.309 0.2730.325h

0.223CH3CN 0.194 0.341f 0.535

0.294CH3NC 0.181 0.235f 0.372

0.063CH3SCN 0.187 0.475f 0.516 0.214

0.216CH3NCS 0.170 0.294f 0.688 0.062

0.532CH3OCN 0.169 0.274f 0.536 0.014

0.288CH3NCO 0.164 0.297f 0.542 0.058

0.407CH3SCH3 0.160 0.486 0.005CH2CH2CH3 0.140f 0.423f

0.130g 0.255gCH3CF3 0.171 0.429f 0.234

0.619CH3CCH 0.176f 0.457f

0.170j 0.1130.354j

CH3NO2 0.162 0.347 0.630 0.0040.263c0.224c,k

CH3F 0.126 0.050 0.327CH3NO 0.150 0.286 0.287 0.122CH3ON 0.152 0.282 0.320 0.494CH3C(O)H 0.160f 0.432f

0.079c 0.015c 0.113CH3Br 0.180 0.590 0.050CH3SeCN 0.188 0.623f 0.455 0.515

0.003CH3NCSe 0.174 0.288f 0.571 0.135

0.201CH3SH 0.165 0.458 0.174 0.138 (S)CH3C(O)OH 0.174 0.462f 0.140c 0.307 (O)

0.005c 0.230eCH3C(O)F 0.180 0.451f 0.256

0.244c 0.079CH3NH2 0.134 0.309 0.574 0.240 (N)CH3PH2 0.158 0.602 0.066 0.030 (P)CH3BH2 0.155 0.251 0.636 0.040 (B)CH3AlH2 0.155 0.403 0.686 0.091 (Al)CH3C(O)NH2 0.166 0.484f 0.436 0.244 (N)

0.072c 0.138CH3C(O)OCH3 0.170 0.460f 0.142


Atom type


Compound Se Br

0.151i 0.048c 0.094c0.316f

CH3PO 0.169 0.625 0.514 0.397CH3OP 0.150 0.278 0.160 0.332CH3C(O)Cl 0.183 0.446f 0.077

0.010c 0.017CH3C(O)CH3 0.161 0.467f 0.090

0.057cCH3PO2 0.198 0.638 0.900 0.429bCH3OPO 0.160 0.331 0.612 0.342

0.387cCH3OF 0.151 0.325 0.069 0.195CH3OS(O)OH 0.161 0.336 0.173

0.383d0.293c0.386e 0.323 (O)

CH3OPO2 0.166 0.298 0.943 0.3300.406b,c

a From MP2 optimized geometries in the TZDP basis set.b Average.c Doubly-bonded atom.d Sulfur.e Hydroxyl.f Methyl.g Methylene.h Middle nitrogen atom.i Methoxy.j Triple bond.k Facing X.

TABLE 12. Mulliken atomic charges calculated at the MP2 level for silicon compoundsa

Atom type

Si H(Si)b B C N O F H(A)Al Si P S Cl

Ge Se BrSn

Compound Pb

SiH3OCH3 0.685 0.092 0.313 0.518 0.141 (C)SiH3NO2 0.584 0.035 0.817 0.167

0.172SiH3ONO 0.639 0.071 0.430 0.445

0.450cSiH3OH 0.676 0.096 0.700 0.312 (O)SiH3Cl 0.543 0.062 0.357SiH3CP 0.575 0.063 0.613 0.226SiH3PC 0.419 0.018 0.589 0.224





Ge Se BrSn

Compound Pb

SiH3CH3 0.526 0.084 0.757 0.162 (C)SiH3SiH3 0.193 0.064SiH3GeH3 0.114 0.061SiH3SnH3 0.039 0.060SiH3PbH3 0.021 0.050SiH4 0.300 0.075SiH3CHCH2 0.537 0.081 0.392 0.116 (C)

0.275f 0.129 (C)SiH3NNN 0.634 0.063 0.558

0.330g0.217

SiH3CN 0.640 0.043 0.095 0.417SiH3NC 0.703 0.050 0.058 0.496SiH3SCN 0.492 0.034 0.236 0.513 0.114SiH3NCS 0.686 0.058 0.613 1.064 0.061SiH3OCN 0.742 0.046 0.293 0.548 0.350SiH3NCO 0.697 0.067 0.438 0.872 0.060SiH3SCH3 0.486 0.066 0.491 0.318 0.173 (C)SiH3CH2CH3 0.504 0.083 0.558f 0.151 (C)

0.454 0.151 (C)SiH3CF3 0.416 0.044 0.408 0.231SiH3CCH 0.647 0.067 0.415h 0.184 (C)

0.217SiH3ONO2 0.662 0.055 0.597 0.375

0.282c0.195c,g

SiH3F 0.905 0.085 0.648SiH3C(O)H 0.449 0.057 0.290 0.077 0.091 (C)SiH3NO 0.559 0.055 0.615 0.221SiH3ONdSiH3Br 0.318 0.052 0.161SiH3SeCN 0.234 0.031 0.008 0.457 0.309SiH3NCSe 0.875 0.080 0.065 0.933 0.234SiH3SH 0.511 0.064 0.480 0.160 (S)SiH3C(O)OH 0.470 0.053 0.284 0.107c

0.215 0.294 (O)SiH3C(O)F 0.466 0.043 0.053 0.025 0.258SiH3NH2 0.651 0.095 0.864 0.253 (N)SiH3PH2 0.330 0.064 0.234 0.149 (P)SiH3BH2 0.341 0.067 0.116 0.012 (B)SiH3AlH2 0.280 0.071 0.075 0.070 (Al)SiH3C(O)NH2 0.438 0.065 0.216 0.391 0.120 0.241 (N)SiH3C(O)OCH3 0.483 0.057 0.272c 0.102c 0.152 (C)

0.324 0.077SiH3OC(O)CH3 0.689 0.070 0.096c 0.481 0.173 (C)

0.464 0.151cSiH3PO 0.239 0.058 0.303 0.386SiH3OP 0.693 0.066 0.226 0.722SiH3C(O)Cl 0.472 0.036 0.273 0.045 0.135


Atom type


Ge Se BrSn

Compound Pb

SiH3C(O)CH3 0.415 0.061 0.204c 0.054 0.162 (C)0.459

SiH3PO2 0.310 0.021 0.645 0.446bSiH3OPO 0.671 0.064 0.643 0.713

0.408cSiH3OF 0.668 0.063 0.292 0.189SiH3OSiH3 0.689 0.086 0.859SiH3OS(O)OH 0.686 0.069 0.533

0.376e0.293c0.355i 0.324 (O)

SiH3OPO2 0.695 0.050 0.938 0.3980.400c,j

a From MP2 optimized geometries in the TZDP basis set.b Average.c Doubly-bonded atom.d Not calculated.e Sulfur.f Methylene.g Middle nitrogen atom.h Attached to Si.i Hydroxyl.j Facing Si.

TABLE 13. Mulliken atomic charges calculated at the MP2 level for germanium compoundsa

Atom type

Ge H(Ge)b B C N O F H (A)Al Si P S Cl

Ge Se BrSn

Compound Pb

GeH3OCH3 0.617 0.065 0.329 0.506 0.138 (C)GeH3NO2 0.491 0.016 0.766 0.160

0.161GeH3ONO 0.531 0.034 0.384 0.249

0.203cGeH3OH 0.589 0.070 0.682 0.303 (O)GeH3Cl 0.498 0.037 0.388GeH3CP 0.441 0.042 0.548 0.231GeH3PC 0.380 0.000 0.594 0.214GeH3CH3 0.472 0.071 0.758 0.166 (C)GeH3SiH3 0.213 0.048GeH3GeH3 0.136 0.045GeH3SnH3 0.001 0.043GeH3PbH3 0.008 0.034





Ge Se BrSn

Compound Pb

GeH4 0.241 0.060GeH3CHCH2 0.438 0.063 0.341 0.122 (C)

0.287e 0.129 (C)GeH3NNN 0.543 0.036 0.513

0.319f0.242

GeH3CN 0.535 0.023 0.111 0.353GeH3NC 0.580 0.026 0.054 0.449GeH3SCN 0.470 0.012 0.215 0.512 0.138GeH3NCS 0.580 0.032 0.517 0.922 0.077GeH3OCN 0.667 0.017 0.250 0.321 0.545GeH3NCO 0.589 0.041 0.379 0.785 0.059GeH3SCH3 0.451 0.046 0.510 0.326 0.177 (C)GeH2CH2CH3 0.488 0.084 0.504e 0.140 (C)

0.421 0.137 (C)GeH3CF3 0.306 0.028 0.462 0.228GeH3CCH 0.467 0.045 0.423g 0.191 (C)

0.099GeH3ONO2 0.576 0.027 0.583 0.319

0.248c0.160c,g

GeH3F 0.796 0.058 0.622GeH3C(O)H 0.356 0.042 0.281 0.055 0.107 (C)GeH3NO 0.454 0.040 0.589 0.256GeH3ON 0.569 0.025 0.449 0.043GeH3Br 0.354 0.029 0.267GeH3SeCN 0.274 0.011 0.002 0.460 0.222GeH3NCSe 0.587 0.038 0.018 0.723 0.230GeH3SH 0.549 0.055 0.528 0.144 (S)GeH3C(O)OH 0.368 0.038 0.264 0.079c

0.204 0.293 (O)GeH3C(O)F 0.440 0.031 0.131 0.139 0.338GeH3NH2 0.567 0.074 0.853 0.255 (N)GeH3PH2 0.319 0.049 0.276 0.052 (P)GeH3BH2 0.296 0.055 0.005 0.122 (B)GeH3AlH2 0.339 0.054 0.069 0.035 (Al)GeH3C(O)NH2 0.331 0.050 0.183 0.390 0.094 0.243 (N)GeH3C(O)OCH3 0.370 0.042 0.236c 0.072c

0.327 0.071 0.154 (C)GeH3OC(O)CH3 0.597 0.042 0.091c 0.437

0.468 0.169c 0.171 (C)GeH3PO 0.208 0.040 0.293 0.381GeH3OP 0.611 0.038 0.187 0.683GeH3C(O)Cl 0.372 0.020 0.254 0.063 0.120GeH3C(O)CH3 0.301 0.045 0.158c 0.039 0.168 (C)

0.474Ge3PO2 0.280 0.005 0.609 0.437Ge3OPO 0.582 0.034 0.582 0.678

0.427c


Atom type


Ge Se BrSn

Compound Pb

GeH3OF 0.588 0.038 0.281 0.195GeH3OSiH3 0.625 0.057 0.671 0.845 0.094 (Si)GeH3O(O)OH 0.597 0.045 0.487

0.355d0.310e0.364h 0.321 (O)

GeH3OPO2 0.627 0.021 0.909 0.652g0.405c0.415c,g

a From MP2 optimized geometries in the TZDP basis set.b Average.c Doubly-bonded atom.d Sulfur.e Methylene.f Middle nitrogen atom.g Facing Ge.h Hydroxyl.

TABLE 14. Mulliken atomic charges calculated at the MP2 level for tin compoundsa

Atom type

Sn H(Sn)b B C N O F H (A)Al Si P S Cl

Ge Se BrSn

Compound Pb

SnH3OCH3 0.803 0.079 0.333 0.628 0.132 (C)SnH3NO2 0.627 0.030 0.856 0.154

0.166SnH3ONO 0.645 0.047 0.396 0.244

0.134cSnH3OH 0.782 0.085 0.821 0.295 (O)SnH3Cl 0.623 0.053 0.464SnH3CP 0.586 0.068 0.620 0.238SnH3PC 0.447 0.021 0.573 0.189SnH3CH3 0.607 0.092 0.806 0.159 (C)SnH3SiH3 0.357 0.072SnH3GeH3 0.332 0.068SnH3SnH3 0.194 0.065SnH3PbH3 0.261 0.058SnH4 0.427 0.107SnH3CHCH2 0.566 0.089 0.410 0.117 (C)

0.286e 0.130 (C)SnH3NNN 0.697 0.048 0.655

0.363f





Ge Se BrSn

Compound Pb

0.261SnH3CN 0.645 0.046 0.216 0.290SnH3NC 0.746 0.047 0.068 0.537SnH3SCN 0.580 0.026 0.200 0.511 0.189SnH3NCS 0.750 0.051 0.624 1.116 0.104SnH3OCN 0.804 0.030 0.233 0.551 0.397SnH3NCO 0.777 0.059 0.346 0.875 0.071SnH3SCH3 0.561 0.062 0.510 0.382 0.172 (C)SnH3CH2CH3 0.570 0.086 0.607e 0.149 (C)

0.460 0.153 (C)SnH3CF3 0.425 0.047 0.376 0.220SnH3CCH 0.676 0.073 0.522g 0.183 (C)

0.118SnH3ONO2 0.710 0.039 0.558 0.359

0.237c0.086c

SnH3F 0.961 0.075 0.736SnH3C(O)H 0.484 0.068 0.336 0.049 0.106 (C)SnH3NO 0.582 0.064 0.655 0.264SnH3ON 0.715 0.042 0.463 0.124SnH3Br 0.503 0.045 0.368SnH3SeCN 0.470 0.027 0.017 0.459 0.085SnH3NCSe 0.762 0.058 0.019 0.828 0.223SnH3SH 0.586 0.063 0.553 0.155 (S)SnH3C(O)OH 0.486 0.060 0.327 0.067c

0.201 0.288 (O)SnH3C(O)F 0.489 0.048 0.103 0.024 0.264SnH3NH2 0.742 0.092 0.960 0.247 (N)SnH3PH2 0.423 0.072 0.306 0.049 (P)SnH3BH2 0.384 0.084 0.002 0.135 (B)SnH3AlH2 0.589 0.107 0.104 0.083 (Al)SnH3C(O)NH2 0.445 0.067 0.257 0.366 0.242 0.242 (N)SnH3C(O)OCH3 0.494 0.064 0.313c 0.057c

0.329 0.064 0.154 (C)SnH3OC(O)CH3 0.711 0.053 0.137c 0.504

0.473 0.226c 0.171 (C)SnH3PO 0.323 0.066 0.254 0.378SnH3OP 0.771 0.050 0.141 0.763SnH3C(O)Cl 0.493 0.036 0.323 0.088 0.149SnH3C(O)CH3 0.413 0.066 0.225c 0.036 0.165 (C)

0.453SnH3PO2 0.385 0.026 0.560 0.432cSnH3OPO 0.714 0.044 0.713 0.749

0.455cSnH3OF 0.762 0.056 0.399 0.196SnH3OSiH3 0.835 0.070 0.641 0.968 0.100 (Si)SnH3OS(O)OH 0.727 0.046 0.548

0.347d0.346c


Atom type


Ge Se BrSn

Compound Pb

0.360h 0.319 (O)SnH3OPO2 0.771 0.029 0.886 0.728g

0.404c0.437c,g

a From MP2 optimized geometries in the TZDP basis set.b Average.c Doubly-bonded atom.d Sulfur.e Methylene.f Middle nitrogen atom.g Facing Sn.h Hydroxyl.

TABLE 15. Mulliken atomic charges calculated at the MP2 level for lead compoundsa

Atom type

Pb H(Pb)b B C N O F H (A)Al Si P S Cl

Ge Se BrSn

Compound Pb

PbH3OCH3 0.765 0.089 0.357 0.547 0.135 (C)PbH3NO2 0.652 0.042 0.861 0.165

0.171PbH3ONO 0.658 0.058 0.412 0.134

0.062cPbH3OH 0.750 0.094 0.751 0.284 (O)PbH3Cl 0.708 0.061 0.524PbH3CP 0.645 0.079 0.634 0.225PbH3PC 0.537 0.031 0.574 0.129PbH3CH3 0.660 0.110 0.838 0.169 (C)PbH3SiH3 0.404 0.092PbH3GeH3 0.355 0.087PbH3SnH3 0.162 0.084PbH3PbH3 0.224 0.075PbH4 0.404 0.101PbH3CHCH2 0.635 0.100 0.458 0.129 (C)

0.267e 0.131 (C)PbH3NNN 0.707 0.053 0.583

0.313f0.277

PbH3CN 0.688 0.053 0.203 0.326PbH3NC 0.726 0.049 0.055 0.524PbH3SCN 0.665 0.034 0.188 0.507 0.246





Ge Se BrSn

Compound Pb

PbH3NCS 0.744 0.050 0.350 0.840 0.103PbH3OCN 0.788 0.030 0.180 0.545 0.332PbH3NCO 0.751 0.061 0.280 0.811 0.037PbH3SCH3 0.652 0.075 0.517 0.426 0.175 (C)PbH3CH2CH3 0.616 0.107 0.641e 0.164 (C)

0.459 0.162 (C)PbH3CF3 0.472 0.062 0.332 0.206PbH3CCH 0.693 0.083 0.425g 0.181 (C)

0.201PbH3ONO2 0.728 0.048 0.561 0.267

0.227c0.016c,g

PbH3F 0.913 0.081 0.669PbH3C(O)H 0.530 0.085 0.364 0.034 0.124 (C)PbH3NO 0.577 0.086 0.612 0.294PbH3ON 0.663 0.057 0.498 0.005PbH3Br 0.614 0.054 0.452PbH3SeCN 0.556 0.035 0.035 0.455 0.037PbH3NCSe 0.738 0.058 0.024 0.735 0.195PbH3SH 0.681 0.076 0.607 0.152 (O)PbH3C(O)OH 0.538 0.075 0.386 0.039c

0.176 0.289 (O)PbH3C(O)F 0.643 0.071 0.021 0.091 0.318PbH3NH2 0.734 0.104 0.925 0.252 (N)PbH3PH2 0.513 0.090 0.355 0.056 (P)PbH3BH2 0.447 0.103 0.178 0.021 (B)PbH3AlH2 0.498 0.101 0.076 0.059 (Al)PbH3C(O)NH2 0.481 0.097 0.301 0.354 0.054 0.256 (N)PbH3C(O)OCH3 0.667 0.097 0.238c 0.174c

0.247 0.152 0.145 (C)PbH3OC(O)CH3 0.722 0.067 0.136c 0.420

0.472 0.279c 0.171 (C)PbH3PO 0.362 0.085 0.255 0.361PbH3OP 0.758 0.057 0.106 0.693PbH3C(O)Cl 0.556 0.050 0.383 0.099 0.123PbH3C(O)CH3 0.458 0.086 0.262c 0.008 0.172 (C)

0.448PbH3PO2 0.435 0.037 0.512 0.418PbH3OPO 0.718 0.054 0.625 0.665

0.516cPbH3OF 0.770 0.067 0.363 0.207PbH3OSiH3 0.798 0.072 0.622 0.892 0.104 (Si)PbH3OS(O)OH 0.748 0.058 0.474

0.335d0.396c0.357h 0.317 (O)


Atom type


Ge Se BrSn

Compound Pb

PbH3OPO2 0.791 0.035 0.875 0.666g0.417c0.479c,g

a From MP2 optimized geometries in the TZDP basis set.b Average.c Doubly-bonded atom.d Sulfur.e Methylene.f Middle nitrogen atoms.g Facing Pb.h Hydroxyl.

TABLE 16. MP2/TZDP calculated dipole moments (in D) for RYa

YnR D H CH3 SiH3 GeH3 SnH3 PbH3F 0. 1.843 1.908 1.374 2.157 2.590 3.433AlH2 0.449 0. 0.552 0.390 0.587 0.725 1.321BH2 0.470 0. 0.552 0.391 0.536 0.719 1.123SH 0.907 1.173 1.605 1.188 1.515 1.738 2.029Br 0. 0.854 1.845 1.466 2.088 2.456 3.030H 0. 0. 0. 0. 0. 0. 0.CCH 0.742 0. 0.730 0.328 0.119 0.287 0.649PH2 0.631 0.656 1.142 0.716 0.733 0.742 0.644NH2 1.939 1.673 1.435 1.283 1.176 1.127 1.350SCH3 1.661 1.604 1.626 1.462 1.536 1.630 1.773Cl 0. 1.234 1.990 1.501 2.241 2.693 3.359NO 0.177 1.695 2.279 2.188 2.087 2.094 1.386ON 0.177 2.700 3.326 b 3.680 3.961 4.017C(O)H 1.551 2.318 2.670 2.170 2.116 2.095 1.856SeCN 3.755 3.743 4.264 4.146 4.412 4.640 4.627NCSe 3.755 1.980 3.730 1.817 3.102 3.745 5.052C(O)F 0.675 2.047 2.854 2.752 2.860 3.092 2.993C(O)NH2 3.552 3.851 3.651 3.430 3.377 3.257 3.152ONO2 0. 2.125 2.933 2.401 3.344 3.685 4.216NCS 2.915 1.991 3.435 2.606 3.607 4.721 4.604SCN 2.915 3.478 4.129 4.031 4.456 4.835 4.944CH2CH3 0.286 0. 0.086 0.775 0.748 0.748 1.007C(O)OH 1.909 1.369 1.568 1.314 1.299 1.344 1.290NO2 0.166 2.537 3.397 3.566 3.973 4.448 4.601ONO 0.166 1.481 2.132 1.274 2.458 2.725 3.006PC 1.020 3.537 5.104 5.491 5.974 6.494 6.912CP 1.020 0.534 1.608 0.408 0.835 1.016 1.327NCO 0.488 2.036 2.855 2.100 2.956 3.645 4.052OCN 0.488 3.853 4.499 4.570 5.456 6.206 6.735CN 2.186 3.013 3.892 3.512 3.964 4.279 4.736NC 2.186 3.283 4.127 3.540 4.367 4.841 5.723



TABLE 16. (continued )YnR D H CH3 SiH3 GeH3 SnH3 PbH3OCH3 1.918 1.705 1.327 1.216 1.226 1.386 1.903CHCH2 0.695 0. 0.332 0.662 0.525 0.470 0.603NNN 0. 1.827 2.356 2.052 2.870 3.552 4.010OH 1.699 1.948 1.705 1.353 1.507 1.670 2.177CH3 0. 0. 0. 0.684 0.614 0.596 0.719SiH3 0.040 0. 0.684 0. 0.144 0.187 0.622GeH3 0.078 0. 0.614 0.144 0. 0.067 0.491SnH3 0.286 0. 0.596 0.187 0.067 0. 0.480PbH3 0.543 0. 0.719 0.622 0.491 0.481 0.CF3 0.361 1.615 2.285 2.316 2.373 2.612 2.305C(O)OCH3 2.618 1.764 1.708 1.605 1.556 1.524 1.642OC(O)CH3 b 1.568 1.708 1.621 1.386 0.931 0.403PO 1.903 2.239 2.796 2.165 2.041 1.970 1.754OP 1.903 1.682 2.222 1.502 2.449 2.999 3.730C(O)Cl 0.259 1.815 2.729 2.844 3.011 3.490 3.363C(O)CH3 2.354 2.670 2.830 2.410 2.310 2.240 2.172PO2 1.347 2.525 3.906 4.096 4.293 4.659 4.703OPO 1.347 1.483 1.782 1.782 2.232 2.185 1.685OF 0.175 1.902 2.296 1.940 2.565 2.986 3.430OSiH3 1.576 1.353 1.216 0.434 1.235 1.857 2.698OS(O)OH 2.610 1.550 2.009 1.474 2.235 2.375 2.641OPO2 0. 3.051 3.987 3.646 4.649 5.117 5.211a At the MP2/TZDP geometry optimized structures. Connectivity is to the leftmost atom in Y.b Not calculated.

Another property calculated in the XH3Y series is the XY bond dissociation energy.For this purpose the MP2 optimized geometries for the XH3 and Y (doublet spin) radicalswere obtained using the unrestricted HF (UHF) method. For comparison to experiment,the electronic energy differences for the reaction

XH3Y ! XH3 C Y 1were converted to enthalpy changes by correcting the electronic energy differences forvibrational, rotational and translational motions at 298 K and adding PV D RTn DC0.6 kcal mol142,43 . Unfortunately, the UHF method does not give an exact eigenfunctionof the spin-squared operator (S 2) and the resultant wave function, upon which the MP2method is based, is contaminated by higher spin states44. If the calculated hS 2i value isclose to the formally exact 0.75 value for a spin doublet electronic state, then the propertiesof the UMP2 wave functions (including energy) are not expected to be significantlyaffected by higher-order corrections. However, where spin contamination is significant(hS 2i > 0.75) in the starting UHF wave function, the UMPn (n D 2, 3, . . .) seriesconverges slowly45 and UMPn theory may give poor results for lower values of n .

A question that arises in using calculated values of ZPE is that of scaling. Experience2,46has shown that HF calculated harmonic vibrational frequencies are usually too large, andthat scaling by an approximate factor of 0.89 generally brings them in good agreementwith experiment. For MP2 calculated frequencies the best fitted scale factor for ZPE isabout 0.9647. For the thermodynamic quantities calculated here no scaling of the ZPEwas imposed. Firstly, a 4% change in a quantity that ranges from 1 6 kcal mol1 asthe difference between products and reactants in an enthalpy of reaction is negligible atthe level of accuracy in these calculations. Secondly, uniform scaling does not guarantee

1. The nature of the CM bond (M D Ge, Sn, Pb) 33uniform accuracy and the possible errors introduced into the ZPE by scaling could belarger than just using the unscaled values48 for this purpose.

Another consideration in calculating bond dissociation energies is basis set superposi-tion error (BSSE). BSSE is defined as the energy resulting from basis functions on eachfragment contributing to the wave function of the other fragment at the equilibrium geom-etry of the molecule in a situation of zero interaction. BSSE is due to incompleteness ofthe Gaussian basis set for each fragment and will tend to enhance the calculated bind-ing energy. A comprehensive discussion of BSSE has recently been given49. One of theadvantages of using the CEP and RCEP methods to eliminate the core electrons is that itsimultaneously reduces the BSSE. It has been shown50 in weakly bonding situations thatthe core electron energy is a large part of the BSSE in all-electron calculations. It is notentirely clear how to define or treat BSSE in a strong bonding situation as in the XH3Yseries. Therefore, BSSE has not been corrected for in this work.

In order to obtain more accurate and reliable values of the calculated bond dissoci-ation energies51,52 a set of diffuse sp-type functions was added to every atom excepthydrogen, where only an additional s-type function was added. The exponents for thesediffuse single Gaussian basis functions were obtained by using the ratio of the small-est two valence orbital exponents of each atom to calculate the diffuse member. Theresultant extended basis set is denoted as TZDP++, and the exponents themselves areshown in Table 2. UMPn n D 2 4 energies in the TZDP++ basis set were calculatedat the UMP2 geometries optimized in the TZDP basis set (MPn/TZDP++//MP2/TZDP)and these were used for all the thermodynamic quantities calculated here. The accu-racy of the MP4 level calculations has recently been discussed53. The HF and UMPnenergies in the extended basis set are tabulated in Tables 17 23. The HY systems wereincluded in these tabulations for completeness. They can be used to generate exchangereaction energies, for example. Calculated zero point energies, without (Table 24) andwith (Table 25) temperature corrections for vibrational, rotational and translational motion,are also listed. Finally, the calculated XH3Y bond dissociation energies are shown inTables 26 30.

TABLE 17. Molecular energies (in au) using the extended basis set (TZDPCC) for radical species Ya

Y UHF UMP2 PUMP2 UMP3 UMP4(SDTQ) hS 2ib

F 23.799767 23.963379 23.964854 23.973230 23.977973 0.7541AlH2 3.024891 3.081404 3.081837 3.094274 3.098228 0.7541BH2 3.765041 3.839410 3.839922 3.854314 3.858453 0.7534SH 10.671916 10.803917 10.805888 10.824419 10.829840 0.7626Br 13.130021 13.239777 13.241001 13.253485 13.256107 0.7569H 0.499819 0.499819 0.499819 0.499819 0.499819 0.7500CCH 11.404284 11.628401 11.645072 11.644639 11.661129 1.0367PH2 7.496066 7.614740 7.616986 7.636813 7.643479 0.7692NH2 10.805899 10.970744 10.972941 10.987004 10.993379 0.7601SCH3 17.332429 17.622118 17.624170 17.653382 17.666810 0.7633Cl 14.655493 14.789473 14.807147 14.810726 14.810726 0.7585NO 25.327962 25.682713 25.687133 25.681919 25.710639 0.7796C(O)H 21.718911 22.050010 22.052610 22.051547 22.078809 0.7665SeCN 24.303562 24.705910 24.713728 24.719332 24.750130 0.8465C(O)F 45.013030 45.546199 45.549424 45.539685 45.579650 0.7758C(O)NH2 32.018545 32.534551 32.536739 32.539828 32.575860 0.7630ONO2 56.520359 57.391503 57.399005 57.340797 57.437639 0.8009NCS 25.259021 25.675797 25.687509 25.695076 25.726215 0.8923



TABLE 17. (continued )Y UHF UMP2 PUMP2 UMP3 UMP4(SDTQ) hS 2ib

CH2CH3 13.854792 14.152235 14.154466 14.183008 14.195935 0.7637C(O)OH 37.442483 37.976993 37.979141 37.974615 38.013598 0.7642NO2 40.946624 41.554124 41.558246 41.528762 41.592847 0.7729CP 11.728528 11.918498 11.950155 11.941271 11.958843 1.5150NCO 30.834362 31.305166 31.313103 31.311167 31.347083 0.8245CN 15.069386 15.326086 15.343146 15.334044 15.357188 1.0128OCH3 22.893201 23.218905 23.221254 23.243824 23.258934 0.7600CHCH2 12.646539 12.906259 12.915173 12.930969 12.945404 0.9056NNN 28.958473 29.449702 29.465278 29.453518 29.496005 0.9056OH 16.232659 16.406306 16.408227 16.418653 16.424830 0.7573CH3 7.191172 7.333512 7.335122 7.352005 7.357752 0.7621SiH3 5.453401 5.552897 5.553452 5.573041 5.578951 0.7545GeH3 5.412748 5.509628 5.510117 5.528667 5.534239 0.7537SnH3 4.982343 5.068931 5.069256 5.086815 5.092287 0.7527PbH3 5.026597 5.114296 5.114812 5.131943 5.137628 0.7541CF3 77.056795 77.805102 77.806004 77.802113 77.843933 0.7543C(O)OCH3 44.093096 44.781817 44.783954 44.790605 44.839330 0.7638OC(O)CH3c 44.132522 44.815447 44.817479 44.819523 44.871642 0.7621PO 22.038067 22.361240 22.363863 22.359775 22.393254 0.7709C(O)Cl 35.839677 36.325336 36.329559 36.333762 36.370096 0.7842C(O)CH3 28.395781 28.880609 28.882872 28.894038 28.928588 0.7642PO2 37.751092 38.298398 38.301842 38.281682 38.335961 0.7739OF 39.399257 39.783029 39.786408 39.789509 39.813737 0.7669OSiH3 21.189909 21.463675 21.465636 21.491555 21.504921 0.7582OS(O)OH 57.705906 58.497428 58.502017 58.486883 58.548781 0.7820OPO2 53.422076 54.186484 54.199172 54.164330 54.236633 0.8577a Geometry optimized at the UMP2/TZDP level. Connectivity is to the leftmost atom in Y.b UHF.c Dissociative to CO2 C CH3.

TABLE 18. Molecular energies (in au) for HY using the extended basis set (TZDP++)a

Y RHF MP2 MP3 MP4(SDTQ)F 24.452342 24.683656 24.683633 24.693973AlH2 3.631450 3.709127 3.725719 3.730307BH2 4.404355 4.506177 4.524671 4.529558SH 11.281142 11.448032 11.469406 11.475702Br 13.731209 13.876241 13.890675 13.894456H 1.132632 1.160186 1.165898 1.167349CCH 12.074921 12.360204 12.371830 12.391149PH2 8.096276 8.243400 8.267926 8.275383NH2 11.436526 11.647833 11.660319 11.668954SCH3 17.937449 18.260876 18.292940 18.307217Cl 15.276903 15.450150 15.467284 15.471667NO 25.864064 26.260593 26.261086 26.291134ON 25.814715 26.183972 26.193043 26.220124C(O)H 22.337551 22

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The Chemistry of Organic Germanium Tin and Lead Compounds Vol-1-1995-Patai