Cundari Th.R. -- Computational Organometallic Chemistry-0824704789

ISBN: 0-8247-0478-9

This book is printed on acid-free paper.

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Preface

This book is intended to fill a gap in the literature by covering a broad range of topics in computational organometallic chemistry. Two objectives were foremost in putting together this volume. First, pedagogical aspects are emphasized throughout. The particular challenges inherent in reliable modeling (quantum or classical) in organometallic chemistry are discussed, and strategies for addressing these challenges are offered. Second, ‘‘how-to’’ aspects are complemented with applications-oriented material covering a wide spectrum of research areas, including catalysis, medicine, organic synthesis, actinide chemistry, and so forth. The first goal will assist those who may have limited experience in computational organometallic chemistry research upon entering this exciting and dynamic field. The second objective will provide motivation for undertaking such an intellectual journey.

Computational Organometallic Chemistry has been written to be accessible to a general scientific audience. These pages will provide upper-division undergraduate students and graduate students with useful lessons that can be employed in their future scientific endeavors, while the applications chapters will spark future research contributions. Similarly, senior researchers, academic and industrial, who may wish to bring their energies to bear on this field will find both

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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

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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 ( )-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(PH3)2Cl, M Rh
	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-C8H8)2 (An Th–Am)	345
	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

Brett M. Bode, Ph.D. Applied Mathematical Sciences, Ames Laboratory, Iowa State University, Ames, Iowa

Bruce E. Bursten, Ph.D. Department of Chemistry, The Ohio State University, Columbus, Ohio

Gyusung Chung, Ph.D. Department of Chemistry, Konyang University,

Chungnam, Korea

Thomas R. Cundari, Ph.D. Department of Chemistry, Computational Research on Materials Institute, The University of Memphis, Memphis, Tennessee

Margaret Czerw, B.A. Department of Chemistry, Rutgers, The State University of New Jersey, New Brunswick, New Jersey

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