New Theoretical Concepts for Understanding Organic Reactions

NATO ASI Series Advanced Science Institutes Series

A Series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological know/edge, with a view to strengthening links between scientific communities.

The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division.

A Life Sciences B Physics

C Mathematical and Physical Sciences

o Behavioural and Social Sciences E Applied Sciences

F Computer and Systems Sciences G Ecological Sciences H Cell Biology

Plenum Publishing Corporation London and New York

Kluwer Academic Publishers Dordrecht, Boston and London

Springer-Verlag Berlin, Heidelberg, New York, London, Paris and Tokyo

Series C: Mathematical and Physical Sciences - Vol. 267

New Theoretical Concepts for Understanding Organic Reactions

edited by

J. Bertran Department of Chemistry, Universitat Autonoma de Barcelona, Spain

and

I. G. Csizmadia Department of Chemistry, University of Toronto, Canada

Kluwer Academic Publishers

Dordrecht / Boston / London

Published in cooperation with NATO Scientific Affairs Division

Proceedings of the NATO Advanced Study Institute on New Theoretical Concepts for Understanding Organic Reactions Sant Feliu de Gufxols, Spain 19June-2July 1988

Library of Congress Cataloging in Publication Data NATO Advanced Study Institute on New Theoretical Concepts for

Understanding Organic Reactions (1988 , San Fellu de Guixols. Spain) New theoretical concepts for understanding organic reactions /

edited by J. Bertran and I.G. Csizoadia. p. ca. -- (NATO ASI series. Series C. Matheaatical and

physical sciences; vol. 267) ·Proceedings of the NATO Advanced Study Institute on New

Theoretical Concepts for Understanding Organic Reactions. Sant Feliu de Guixols. Spain. 19 June-2 July. 1988.·

Includes index. 1. Cheaistry. Physical and theoretical--Congresses. 2. Che.istry.

Organic--Congresses. I. Bertran. J. (Juan). 1931-II. Csizaadia. I. G. III. Title. IV. Series: NATO ASI series. Series C. Mathenatical and phvslcal sciences; no. 267. Q0476.N38 1988 547.1--dcI9 89-2824

ISBN-13: 978-94-010-7539-8 e-ISBN-13: 978-94-009-2313-3 001: 10.1007/978-94-009-2313-3

Published by Kluwer Academic Publishers, P.O. Box 17, 3300 AA Dordrecht, The Netherlands.

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All Rights Reserved © 1989 by Kluwer Academic Publishers Softcover reprint of the hardcover 1 st edition 1989

No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo­copying, recording or by any information storage and retrieval system, without written permission from the copyright owner.

TABLE OF CONTENTS

Foreword Organizing Comittees List of Lecturers and Tutors List of Participants

I.G. Csizmadia Multidimensional theoretical stereochemistry and conformational potential energy surface topology

H. Bernhard Schlegel Some practical suggestions for optimizing geometries and locating transition states

Paul G. Mezey Reaction topology and quantum chemical molecular design on potential energy surfaces

Paul G. Mezey Topology of molecular shape and chirality

M.A. Robb and F. Bernardi Adiabatic and diabatic surfaces in the treatment of chemical reactivity. I. Theory

F. Bernardi, M. Olivucci and M.A. Robb Adiabatic and diabatic surfaces in the treatment of chemical reactivity. II. An illustrative application to the Diels Alder reaction

vii ix

xi xv

33

ss

77

101

147

vi

Sason S. Shaik A qualitative valence bond model for organic reactions

Jean Louis Rivail Solvent effects on potential energy surfaces and chemical kinetics

Juan Bertran Modifications of potential energy surfaces by solvation and catalysis

F.A. Gianturco Computational tests of potential energy surfaces from dynamical properties

Susan C. Tucker and Donald G. Truhlar Dynamical formulation of transition state theory: variational transition states and semiclassical tunneling

William H. Miller Theoretical models for reaction dynamics in polyatomic molecular systems

A. Bottoni, M. Duran, J.M. Lluch and M.R. Peterson Practical applications of new theoretical concepts in organic chemistry

Subject Index

165

219

231

257

291

347

373

387

FOREWORD

People who attended the NATO Advanced Study Institute (ASI) entitled NEW THEORETICAL CONCEPTS FOR UNDERSTANDING ORGANIC REAC­TIONS held at Sant Feliu de Gufxols on the Costa Brava of Spain had a unique experience. They have seen the evolution of the field from qualitative arguments through the generation of Potential Energy Surfaces (PES) to the use of PES in molecular dynamics. The excellent lectures that were dedicated to the various aspects of Potential Energy Surfaces clearly revealed a colossal amount of ma­terial that represents our current understanding of the overall problem. It is our hope that the present volume will recreate the excitement in the readers that we all experienced during the meeting in Spain.

One can say, without too much exaggeration, that chemistry has become and exercise on potential energy surfaces (PES). Structural (position of the energy minima), spectroscopic (vicinity around the minima), and reactivity (reaction path along the surface) properties may be determined from the analysis of PES. New theoretical tools, together with recent developments in computer technology and programming, have allowed to obtain a better knowledge of these surfaces, and to extract further chemical information from them, so new horizons have been added to Theoretical Organic Chemistry.

This book collects contributions that review the latest advances of theoreti­cal concepts for the study of organic reactions in terms of mathematical, com­putational and interpretative methods. In particular, it collects topics such as interpretation of PES, computation of stationary points, diabatic and adiabatic PES, reaction topology, solvent effect and catalysis, reactivity patterns, validity of transition state theory, molecular dynamics and reaction path models.

vii

viii

Needless to say, the success of any International Meeting depends on a num­

ber of people, and the present ASI is no exception. This meeting highly succeeded

owing to the hard work of the members of the International and Local Organizing

Commitees, to the bright interventions of Lecturers and Tutors, and to the huge

enthousiasm exhibited by all Participants. We must thus thank very much all

those people. Last but not least, we must thank especially NATO for its spon­

sorship and for providing the financial support required to complete successfully

this Advanced Study Institute.

J. Bertran

I. G. Csizmadia

November 10, 1988

INTERNATIONAL ORGANIZING COMMITTEE

Prof. Juan BERTRAN

Prof. Paul G. MEZEY

Prof. Michael A ROBB

Prof. Antonio OLIVA

Departament de Quimica Facultat de Ciencies Universitat Autonoma de Bar'celona 08193 Bellaterra (Barcelona) SPAIN

Department of Chemistry University of Saskatchewan Saskatoon, Saskatchewan CANADA S7B OWO

Department of Chemistry King's College London Strand London WC2R 2LS England

Departament de Quimica Facultat de Ciencies Universitat Autonoma de Barcelona 08193 Bellaterra (Barcelona) SPAIN

LOCAL ORGANIZING COMMITTEE

Prof. Juan BERTRAN

Prof. Antonio OLIVA

Dr. Jose M" LLUCII

Dr. Hiqucl DURAN

Dr. Agusti LLEDOS

Ms. Angels GONZALEZ-LAFONT

Hs. ~1a pj una SODUPE

J'.I [' • l>1iquel SOLA

~1s • Joana MARTINEZ, Secpetary

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LIST OF LECTURERS

Prof. Fernando BERNARDI

Prof. Juan BERTRAN

Prof. Imre G. CSIZMADIA

Pr0f. Franco A. GIANTURCO

Prof. Paul G. MEZEY

Prof. William H. MILLER

Prof. Jean-Louis RIVAIL

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Dipartamento di Chimica Universita di Bologna Via Selmi, 2 40126 BOLOGNA ITALY

Departament de Quimica Facultat de Ciencies Universitat Autonoma de Barcelona 08193 Bellaterra (Barcelona) SPAIN

Department of Chemistry University of Toronto 80, St. George Street Toronto, Ontario CANADA M5S 1A1

Dipartimento di Chimica Universita di Roma "La Sapienza" Citta Universitaria 008185 Roma ITALY

Department of Chemistry University of Saskatchewan Saskatoon, Saskatchewan CANADA S7N OWO

Department of Chemistry University of California Berkeley, California 94720 USA

Laboratoire de Chimie Theorique Universite de Nancy I B.P. 239 54506 Vandoeuvre-Les-Nancy Cedex FRANCE

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Prof. Michael A. ROBB

Prof. SASON S. SHAIK

Prof. II. Bernhard SCHLEGEL

Prof. Paul v.R. SCHLEYER

Pruf. Donald G. TRUHLAR

LIST OF TUTORS

Dr. Andrea BOTTONI

Department of Chemistry King's College London Strand London WC2R 2LS ENGLAND

Department of Chemistry Ben-Gurion University of the Negev P.O.B. 653 Beer-Sheva 84105 ISRAEL

Department of Chemistry Wayne State University Detroit, Michigan 48202 USA

InstitUt fUr Organische Chemie Universitat Erlangen -Nlirnberg Henkestrasse, 42 8520 Erlangen FED. REP. GERMANY

Department of Chemistry University of Minnesota 207, Pleasant Street S.E. Minneapolis, Minnesot,a 55455 USA

Dipartimento di Chimica Universita di Bologna Via Selmi, 2 40126 Bologna ITALY

Dr. Miquel DURAN

Dr. Jos~ M~ LLUCH

Dr. Mike R. PETERSON

Departament de QU1mica Facultat de Ciencies Universitat Autonoma de Barcelona

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08193 Bellaterra (Barcelona) SPAIN

Departament de QU1mica Facultat de Ciencies Universitat Autonoma de Barcelona 08193 Bellaterra (Barcelona) SPAIN

Department of Chemistry University of Toronto Toronto, Ontario M5S lAl CANADA

LIST OF PARTICIPANTS

Mr. Carlo ADAMO

Mr. Manuel ALCAMI

Dr. Pietro AMODEO

Dr. Juan ANDRES

Dr. Janos G. ANGYAN

Mr. Luis ARNAUT

Dr. Gustavo ARTECA

Dr. Carmen BARRIENTOS

Dipartimento de Chimica Universita di Napoli Via Mezzocanone, 4 80134 Napoli ITALY

Departamento de Quimica (C-XIV) Universidad Aut6noma de Madrid Cantoblanco 28049 MADRID SPAIN

Dipartimento de Chimica Universita di Napoli Via Mezzocanone, 4 80134 Napoli ITALY

Departament de Quimica Fisica Universitat de Valencia Dr. Moliner, 50 46100 Burjassot (Valencia) SPAIN

Chinoin Research Centre P.O. BOX 110 H-1325 Budapest HUNGARY

Departamento de Quimica Universidade de Coimbra 3045 Coimbra PORTUGAL

Department of Chemistry University of Saskatchewan Saskatoon, Saskatchewan CANADA S7N OWO

Departamento de Quimica Fisica Facultad de Ciencias Universidad de Valladolid 47005 Val12dolid SPAIN

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Dr. Jean-Claude BARTHELAT

Ms. Laura BONATI

Ms. Michelle CARNELL

Dr. Allen CLABO

Ms. M. N. D. S. CORDEIRO

Ms. Betty COUSSENS

Mr. Gary FOX

Dr. Franca FRATERNALI

Universite Paul Sabatier 118, route de Narbonne 31062 Toulouse Cedex FRANCE

Dipartimento di Chimica Fisica Universita di Milano Via Golgi, 19 20133 Milano ITALY

Lehrstuhl fUr Theoretische Chemie Universitat Bonn Wegelerstrasse 12 0-5300 Bonn F.R. GERMANY

InstitUt fUr Organische Chemie Universitat Erlangen­NUrnberg Henkestrasse 42 0-8520 Erlangen F.R. GERMANY

Faculdade de Ciencias Universidade do Porto Pra9a Gomes Teixeira 4000 Porto PORTUGAL

Department of Chemistry University of Leuven Celestijnenlaan 200F 3030 Heverlee BELGIUM

Department of Chemistry Wayne State University Detroit, Michigan 48202 USA

Dipartimento di Chimica Universita di Napoli Via Mezzocanone 4 80134 Napoli ITALY

Dr. J. Luis GARCIA de PAZ

Dr. Carlo GATTI

Dr. Jose A.N.F. GOMES

Dr. Alfonso HERNANDEZ-LAGUNA

Dr. Miriam KARNI

Dr. Alessandro LAMI

Dr. Antonio LARGO-CABRERIZO

Dr. Adriana LISINI

Departamento de Quimica (C-XIV) Universidad Aut6noma de Madrid Cantoblanco 28049 Madrid SPAIN

Dipartimento di Chimica Fisica Centro del C.N.R. Via Golgi, 19 20133 Milano ITALY

Faculdade de Ciencias Universidade do Porto Pra~a Gomes Teixeira 4000 Porto PORTUGAL

Instituto de Estructura de la Materia Serrano, 119 28006 MADRID SPAIN

Technion Israel Institute of Technology Haifa 32000 ISRAEL

xvii

Istituto di Chimica Quantica Via Risorgimento 35 56100 Pisa ITALY

Departamento de Quimica Fisica Facultad de Ciencias Universidad de Valladolid 47005 Valladolid SPAIN

Dipartimento di Scienze Chimiche Universita di Trieste Piazzale Europa, 1 34127 Trieste ITALY

xviii

Dr. Rafael LOPEZ-FERNANDEZ

Mr. John F. MARCOCCIA

Ms. Maria-Isabel MENENDEZ

Ms. Camilla MINICHINO

Mr. Victor M.S. MORAIS

Dr. Giorgio MORO

Mr. Ricardo A. MOSQUERA

Ms. Fabrizia NEGRI

Departamento de Quimica (C-XIV» Universidad Autonoma de Madrid Cantoblanco 28049 Madrid SPAIN

Department of Chemistry University of Toronto Toronto, Ontario CANADA M5S 1A1

Departamento de Quimica Fisica Universidad de Oviedo 33007 OVIEDO SPAIN

Istituto di Chimica Universita della Basilicata Via Nazario Sauro, 85 85100 Potenza ITALY

Av. Inf. D. Henrique 450 4400 Vila Nova de Gaia PORTUGAL

Dipartimento di Chimica Fisica Universita di Milano Via Golgi, 19 20133 Milano ITALY

Departamento de Quimica Fisica Facultad de Quimica Av. de las Ciencias 15706 Santiago de Compostela SPAIN

Dipartimento di Chimica Universita di Bologna Via Selmi, 2 40126 Bologna ITALY

Dr. Mint-Tho NGUYEN

Dr. Cemil OGRETIR

Mr. Massimo OLIVUCCI

Dr. Fulvia ORSINI

Mr. Alberto A.C.C. PAIS

Mr. Juan-Luis PASCUAL-AHUIR

Dr. Demetrio PITEA

Dr. Jose-Joaquin QUIRANTE

Department of Organic Chemistry University of Groningen Nijenborgh 16 9747 AG Groningen THE NETHERLANDS

Department of Chemistry Faculty of Arts and Sciences Anadolu University 26470 Eskisehir TURKEY

Dipartimento di Chimica Universita di Bologna Via Selmi, 2 40126 Bologna ITALY

Dipartimento di Chimica Organica C.N.R. Via Venezian, 21 20133 Milano ITALY

Departamento de Quimica Universidade de Coimbra 3049 Coimbra PORTUGAL

Departamento de Quimica Fisica Universitat de Valencia Dr. Moliner, 50 46100 Burjassot (Valencia) SPAIN

Dipartimento di Chimica Fisica Universita di Milano Via Golgi, 19 20133 Milano ITALY

Departamento de Quimica Fisica Universidad de Malaga Campus de Teatinos 29071 Malaga SPAIN

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Dr. Sachchida N. RAI

Mr. Willi REUTER

Dr. Isabel ROZAS

Ms. Beverly A. RUF

Dr. Enrique SANCHEZ-MARCOS

Mr. Ramon SAYOS

Dr. Guido SELLO

Dr. Thomas SCHONHERR

Theoretische Chemie Bergische Universitat Gauss Str. 20 5600 Wuppertal F.R. GERMANY

LehrstUhl flir Theoretische Chemie Universitat Bonn Wegelerstrasse 12 D-5300 Bonn F.R. GERMANY

Instituto de Quimica Medica Juan de la Cierva, 3 28006 Madrid SPAIN

Department of Chemistry University of California Berkeley, California 94720 USA

Departamento de Quimica Fisica Universidad de Sevilla Tramontana, sin 41012 Sevilla SPAIN

Departament de Quimica Fisica Universitat de Barcelona Av. Diagonal, 647 08028 Barcelona SPAIN

Dipartimento di Chimica Organica Universita di Milano Via Venezian 21 20133 Milano ITALY

Institut fUr Theoretische Chemie Universitatsstr. 1 D-4000 DUsseldorf F.R. GERMANY

Mr. Hanoch SENDEROWITZ

Ms. Suzi TUCKER

Dr. Jesus M. UGALDE

Dr. Petros VALTAZANOS

Ms. Corinne VAUGHAN

Mr. Saulo VAZQUEZ

Mr. Malte von ARNIM

Mr. Peng WANG

Dr. Ian WILLIAMS

School of Chemistry Tel-viv University Ramat-Aviv 69978 Tel-Aviv ISRAEL

Department of Chemistry University of Minnesota 207 Pleasant Street S.E. Minneapolis, Minnesota 55455 USA

Kimika Fakultatea

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Euskal Herriko Unibertsitatea Posta Kutxa 1072 20080 Donostia SPAIN

National Hellenic Research Foundation 48, Vas. Constantinou Athens 11635 GREECE

King's College Strand London WC2R 2LS ENGLAND

Departamento de Quimica Fisica Universidad de Santiago Av. de las Ciencias sin 15706 Santiago de Compostela SPAIN

Lehrstuhl fUr Theoretische Chemie Universitat Bonn Wegelerstrasse 12 D-5300 Bonn F.R. GERMANY

Department of Chemistry University of California Berkeley, California 94720 USA

School of Chemistry University of Bristol Bristol Bs8 ITS ENGLAND