Computational Organometallic Chemistry

441 Pages·2001·4.61 MB·English

by  Thomas R. Cundari

ISBN:0-8247-0478-9
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Preface
This book is intended to fill a gap in the literature by covering a broad range
oftopics incomputationalorganometallic chemistry.Two objectives werefore-
most in putting together this volume. First, pedagogical aspects are emphasized
throughout.Theparticularchallengesinherentinreliablemodeling(quantumor
classical)inorganometallicchemistryarediscussed,andstrategiesforaddressing
thesechallengesareoffered.Second,‘‘how-to’’aspectsarecomplementedwith
applications-orientedmaterialcoveringawidespectrumofresearchareas,includ-
ing catalysis, medicine, organic synthesis, actinide chemistry, and so forth. The
first goal will assist those who may have limited experience in computational
organometallicchemistryresearchuponenteringthisexcitinganddynamicfield.
Thesecondobjectivewillprovidemotivationforundertakingsuchanintellectual
journey.
ComputationalOrganometallicChemistryhasbeenwrittentobeaccessible
to a general scientific audience. These pages will provide upper-division under-
graduatestudentsandgraduatestudentswithusefullessonsthatcanbeemployed
in their future scientific endeavors, while the applications chapters will spark
futureresearchcontributions.Similarly,seniorresearchers,academicandindus-
trial, who may wish to bring their energies to bear on this field will find both
iii
iv Preface
motivation and suitable background to do so. To accomplish these ambitious
goals, an internationally recognized group of experts has been assembled, each
focusing on his or her particular area of expertise within this growing field of
science.
Thomas R. Cundari
Contents
Preface iii
Contributors ix
1. Introduction 1
Thomas R. Cundari
2. Recipe for an Organometallic Force Field 7
Per-Ola Norrby
3. Computational Approaches to the Quantification of Steric
Effects 39
David P. White
4. The Accuracy of Quantum Chemical Methods for the
Calculation of Transition Metal Compounds 69
Michael Diedenhofen, Thomas Wagener, and Gernot Frenking
v
vi Contents
5. Nondynamic Correlation Effects in Transition Metal
Coordination Compounds 123
Kristine Pierloot
6. Quantitative Consideration of Steric Effects Through Hybrid
Quantum Mechanics/Molecular Mechanics Methods 159
Feliu Maseras
7. HIV Integrase Inhibitor Interactions with Active-Site Metal
Ions: Fact or Fiction? 185
Abby L. Parrill, Gigi B. Ray, Mohsen Abu-Khudeir, Amy Hirsh
and Angela Jolly
8. Cyclometallation of a Computationally Designed Diene:
Synthesis of ((cid:1))-Androst-4-ene-3,16-dione 205
Douglass F. Taber, James P. Louey, Yanong Wang, and
Wei Zhang
9. Rhodium-Mediated Intramolecular C–H Insertion: Probing the
Geometry of the Transition State 217
Douglass F. Taber, Pascual Lahuerta, James P. Louey, Scott
C. Malcolm, Robert P. Meagley, Salah-eddine Stiriba, and
Kimberly K. You
10. Molecular Mechanics Modeling of Organometallic Catalysts 237
David P. White and Warthen Douglass
11. Titanium Chemistry 275
Mark S. Gordon, Simon P. Webb, Takako Kudo, Brett M. Bode,
Jerzy Moc, Dmitri G. Fedorov, and Gyusung Chung
12. Spin-Forbidden Reactions in Transition Metal Chemistry 291
Jeremy Noel Harvey
13. Oxidative Addition of Dihydrogen to M(PH)Cl, M (cid:2) Rh
3 2
and Ir: A Computational Study Using DFT and MO Methods 323
Margaret Czerw, Takeyce K. Whittingham, and Karsten
Krogh-Jespersen
14. The Electronic Structure of Organoactinide Complexes via
Relativistic Density Functional Theory: Applications to the
Contents vii
Actinocene Complexes An(η8-CH) (An (cid:2) Th–Am) 345
8 8 2
Jun Li and Bruce E. Bursten
15. Pi Bonding in Group 13–Group 15 Analogs of Ethene 381
Ashalla McGee, Freida S. Dale, Soon S. Yoon, and Tracy P.
Hamilton
16. Main Group Half-Sandwich and Full-Sandwich Metallocenes 397
Ohyun Kwon and Michael L. McKee
Index 425

Contributors
Mohsen Abu-Khudeir, B.S. Department of Chemistry, The University of
Memphis, Memphis, Tennessee
BrettM.Bode,Ph.D. AppliedMathematicalSciences,AmesLaboratory,Iowa
State University, Ames, Iowa
BruceE.Bursten,Ph.D. DepartmentofChemistry,TheOhioStateUniversity,
Columbus, Ohio
Gyusung Chung, Ph.D. Department of Chemistry, Konyang University,
Chungnam, Korea
Thomas R. Cundari, Ph.D. Department of Chemistry, Computational Re-
searchonMaterialsInstitute, TheUniversity ofMemphis, Memphis,Tennessee
MargaretCzerw,B.A. DepartmentofChemistry,Rutgers,The StateUniver-
sity of New Jersey, New Brunswick, New Jersey
ix