Fundamental and Technological Aspects of Organo-f-Element Chemistry PDF
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Fundamental and Technological Aspects of Organo-f-Element Chemistry NATO ASI Series Advanced Science Institutes Series A series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, 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 Plenum Publishing Corporation B Physics London and New York C Mathematical D. Reidel Publishing Company and Physical Sciences Dordrecht, Boston and Lancaster D Behavioural and Social Sciences Martinus Nijhoff Publishers E Engineering and The Hague, Boston and Lancaster Materials Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York and Tokyo Series C: Mathematical and Physical Sciences Vol. 155 Fundamental and Technological Aspects of Organo-f-Element Chemistry edited by Tobin J. Marks Department of Chemistry, Northwestern University, Evanston, Illinois, U.S.A. and Ignazio L. Fragala Department of Chemistry, University of Catania, Catania, Italy D. Reidel Publishing Company Dordrecht / Boston / Lancaster Published in cooperation with NATO Scientific Affairs Division Proceedings of the NATO Advanced Study Institute on Fundamental and Technological Aspects of Organo-f-Element Chemistry Acquafredda di Maratea, Italy September 10-21, 1984 Library of Congress Cataloging in Publication Data NA TO Advanced Study I nstitute on Fundamental and Technological Aspects of Organo f-Element Chemistry (1984: Aquafredda di Maratea, Italy) Fundamental and technological aspects of organo-f-element chemistry. (NATO ASI series. Series C, Mathematical and physical sciences; vol. 153) "Proceedings of the NATO Advanced Study Institute on Fundamental and Techno logical Aspects of Organo-f-Element Chemistry, Acquafredda di Maratea, Italy, September 10-21, 1984"-T.p.verso. "Published in cooperation with NATO Scientific Affairs Division." Includes index. Contents: Organolanthanoides 1 Herbert Schumann - 4f-elements in organic synthesis 1 H. B. Kagan - (8)annulene derivatives of actinides and lanthanides 1 Andrew Streitweiser, Jr. and Steven A. Kinsley - (etc.) 1. Organometallic compounds-Congresses. 2. Rare earth metal compounds Congresses. 3. Actinide compounds-Congresses. I. Marks, Tobin J. II. Fragala, Ignazio L. (Ignazio Luciano), 1943- . III. North Atlantic Treaty Organization. Scientific Affairs Division. IV. Title. V. Series. QD410.N36 1984 547'.05 85-8400 ISBN-13: 978-94-010-8887-9 e-ISBN-13: 978-94-009-5406-9 001: 10.1007/978-94-009-5406-9 Published by D. Reidel Publishing Company PO. Box 17,3300 AA Dordrecht, Holland Sold and distributed in the U.S.A. and Canada by Kluwer Academic Publishers, 190 Old Derby Street, Hingham, MA 02043, U.S.A. In all other countries, sold and distributed by Kluwer Academic Publishers Group, PO. Box 322, 3300 AH Dordrecht, Holland D. Reidel Publishing Company is a member of the Kluwer Academic Publishers Group All Rights Reserved © 1985 by D. Reidel Publishi ng Company, Dordrecht, Holland. Softcover reprint of the hardcover 1st edition 1985 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 vii List of Participants ~x ORGANOLANTHANOIDES: REVIEW AND NEW DEVELOPMENTS Herbert Schumann 4f-ELEMENTS IN ORGANIC SYNTHESIS H. B. Kagan 49 [8]ANNQLENE DERIVATIVES OF ACTINIDES AND LANTHANIDES Andrew Streitwieser, Jr. and Steven A. Kinsley 77 ACTINIDE HYDROCARBYL AND HYDRIDE CHEMISTRY Tobin J. Marks and Victor W. Day 115 ORGANOACTINIDE COMPLEXES CONTAINING CLASSICAL LIGANDS Josef Takats 159 FRONTIER ELEMENTS: CONNECTIONS WITH f-ELEMENTS Jan H. Teuben 195 ELECTRONIC STRUCTURE AND OPTICAL SPECTROSCOPY OF fn IONS AND COMPOUNDS Norman Edelstein 229 NMR-SPECTROSCOPY OF ORGANO-f-ELEMENT AND PRE-LANTHANOID COMPLEXES: SOME CURRENT TRENDS R. Dieter Fischer 277 PHOTOELECTRON SPECTROSCOPY OF f-ELEMENT ORGANOMETALLIC COMPLEXES Ignazio L. Fragala and Antonio Gulino 327 f-ELEMENT PHOTOCHEMISTRY P. Bergamini, S. Sostero, and o. Traverso 361 NEW PERSPECTIVES OF LANTHANIDES IN CATALYSIS Mario Bruzzone and Atonio Carbonaro 387 Appendix 401 Index 405 FOREWORD The past decade has seen a dramatic acceleration of activity and interest in phenomena surrounding lanthanide and actinide organo metallic compounds. Around the world, active research in organo-f element synthesis, chemistry, catalysis, crystallography, and quantum chemistry is in progress. This activity has spanned a remarkably wide range of disciplines, from synthetic/mechanistic inorganic and organic chemistry to radiochemistry, catalytic chemistry, spectroscopy (vibra tional, optical, magnetic resonance, photoelectron, Mossbauer), X-ray and neutron diffraction structural analysis, as well as to crystal field and molecular orbital theoretical studies at the interface of chemistry and physics. These investigations have been motivated both by fundamental and applied goals. The evidence that f-element organo metallic compounds have unique chemical and physical properties which cannot be duplicated by organometallic compounds of d-block elements has suggested many new areas of endeavor and application. For these reasons, a great many scientists felt the need for some international forum devoted exclusively to the subject of lanthanide and actinide organometallic compounds. In September of 1978, a NATO Advanced Study Institute entitled, "Organometallics of the f-Elements," was held at the SOGESTA Conference Center near Urbino, Italy. It was the universal feeling of the partic ipants that this first meeting was a great success and that vital international communication and collaboration had been stimulated. The principal lectures at this Institute were published by Reidel in 1979 as part of the NATO ASI Monograph Series ("Organometallics of the f-Elements," T. J. Marks and R. D. Fischer, editors). The need for a second such Institute at a later date was made espe cially clear by the success of the SOGESTA meeting, by the rapid scien tific advances that were being achieved, and by the enthusiastic response of over 100 prospective participants who were polled. The result was the NATO Advanced Study Institute, "Fundamental and Techno logical Aspects of Organo-f-Element Chemistry," held September 10-21, 1984, in Acquafredda di Maratea, Italy. In organizing the program for this meeting, it was decided to modify the content considerably vis-a vis the 1978 conference. It was desired to incorporate the major advances that had been achieved in synthesis and reaction mechanism, to address the growing industrial interest in this area, and to better integrate the developing phenomenology with what was known about related, but non-f, "frontier" elements. The Institute brought together a group of over 90 highly qualified lecturers and students from a large number of countries and sought to assemble in 12 days of lectures, seminars, poster sessions, and discussions (both formal and informal), a comprehensive and meaningful picture of what is currently known about organo-f-element compounds. It was the enthusiastic con sensus of the participants that this goal was achieved. The chapters of the present monograph represent a compilation of the principal lectures delivered at "Fundamental and Technological Aspects of Organo-f-Element Chemistry." They are arranged in approxi mately the same order in which they were presented, and strive to con- vii viii FOREWORD vey as complete and comprehensible a picture as the current state of knowledge and practical space limitations will permit. The chapter authors have been given a great deal of freedom in preparing their contributions so that personal viewpoints could be presented and so that new, unpublished results could be disseminated. In addition to these chapters, the program of the Institute included introductory lectures on the f-elements and on basic organometallic chemistry, as well as a number of contributed lectures and posters. The titles and authors of these contributions are given in the Appendix to this volume. A number will be published in a special issue of Inorganica Chimica Acta. Neither the Institute nor this monograph would have been possible without the generous help and support of a number of people and organi zations. The advice and financial support of the NATO Division of Scientific Affairs (Drs. Craig Sinclair and Mario di Lullo) was of course essential. Travel and/or lodging grants for students and other organizational funds were also generously provided by the AERE (Canada), Assoreni (Italy), the Province of Basilicata (Italy), the CNR (Italy), the CNRS (France), the DAAD (West Germany), the DFG (West Germany), Imperial Chemical Industries (U.K.), the NSF (U.S.A.), Pergamon Press, Ltd. (U.K.), and Rhone-Poulenc Chemical Co. (France). We also appreciate the efforts of those who were able to reduce the financial burden on the Institute by obtaining financial assistance from their universities, companies, governments, etc. We acknowledge as well the other members of our organizing committee, Dr. Mario Bruzzone (Assoreni), Prof. R. Dieter Fischer (U. of Hamburg), and Prof. Josef Takats (U. of Alberta) for their invaluable assistance in making this ASI a success. The management and staff of the Hotel Villa del Mare are to be thanked for their efficient, responsive service and warm hospitality, which contributed to everyone's enjoyment of the Institute. D. Reidel Publishing Company has provided the materials and advice necessary for the rapid assembly and production of this volume. Mrs. N. M. Pols-v.d. Heijden of their staff is to be thanked for this essential service. Finally, we will be forever grateful to Mrs. Vonita Curbow, without whose unflagging secretarial support, "Fundamental and Technological Aspects of Organo-f-Element Chemistry" could never have been brought to fruition. To the Maratea ASI veterans, we convey our sincere thanks for their enthusiastic participation and our best wishes. Tobin J. Marks Ignazio L. Fragal~ (director) (co-director) Evanston and Catania January, 1985 LIST OF PARTICIPANTS William Beeckman Dr. Chen Wenqi Universite de Liege Changchun Inst. of Applied Chem. Institut de Physique Changchun, Jilin B5 Universite de Liege Av PEOPLE'S REPUBLIC OF CHINA Sart Tilman-B.4000 Liege BELGIUM Prof. Pekka Pyykko Department of Chemistry Prof. J. Goffart University of Helsinki Chimie Analytique et Radoichimie Et. Hesperiankatu 4 Universite de Liege 00100 Helsinki, FINLAND B-4000 Sart Tilman - Liege BELGIUM Prof. Michel Bonnet Institut de Recherches sur Prof. M. R. Spirlet la Catalyse University of Liege 2 Avenue A. Einstein Institut de Physique 69626 Villeurbanne Cedex Edmonton, Alberta FRANCE CANADA 76G 2G2 Prof. Gerard Folcher Dr. Patricia MacNeil Commissariat a l'Energie Department of Chemistry Atomique, Departement de University of British Columbia Physico-Chimie CEN-Saclay 2036 Main Mall 91191 Gif-Sur-Yvette CEDEX Vancouver, B.C. V6T lY6 CANADA FRANCE Dr. F. Matisons Dr. C. Giannotti Department of Chemistry ICSN-CNRS University of British Columbia 91190 Gif-sur-Yvette FRANCE 2036 Main Mall Vancouver, B.C. V6T lY6 CANADA Professor H. B. Kagan Laboratoire de Synthese Dr. M. Mlekuz Asymetrique, (LA 255) Department of Chemistry Universite Paris-Sud McMaster University 91405 Orsay FRANCE Hamilton, Ontario, CANADA L8S 4Ml Dr. J. F. LeMarechal Department of Physico-chimie Dr. M. Stainer CEN-Saclay Department of Chemistry 91191 Gif/Yvette - Cedex FRANCE University of Toronto Toronto, Ont. CANADA Dr. Jean-Louis Namy Laboratoire de Synthese Prof. Josef Takats Asymetrique, Department of Chemistry Universite Paris Sud University of Alberta Bat 420 Faculte de Scineces Edmonton, Al tao , 91405 Orsay, FRANCE CANADA T6G 2El ix x LIST OF PARTICIPANTS Mr. Martin Adam Mr. Detlef F. Hohl Institut fur Anorganische Lehrstuhl F. Theoretische Chemie und Angewandte Chemie Technische Universitat Kunchen Universitat Hamburg Lichtenbergstrasse 4 Martin-Luther-King-Platz 6 D-8046 Garching WEST GERMANY 2000 Hamburg 13 WEST GERMANY Mr. Siegbart Nickel Dr. lIse Albrecht Technische Universitat Berlin Technische Universitat Eerlin Strasse des 17 Juni 135 Strass des' 17 June 135 1000 Berlin 12 WEST GERMANY 1000 Berlin 12 WEST GERMANY Dr. Wolfgang Oroschin Dr. H.-D. Amberger Institut fur Anorganische Chemie Institut fur Anorganische Universitat Hamburg und Angewandte Chemie Martin-Luther-King-Platz 6 Universitat Hamburg 2000 Hamburg 13 WEST GERMANY Martin-Luther-King-Platz 6 2000 Hamburg 13 WEST GERMANY Professor NObker ROsch Lehrstuhl F. Theoretische Chemie Mr. Michael Bickel Technische Universitat Kunchen Nuclear Research Center Karlsruhe Lichtenbergstrasse 4 Institut fur Heisse Chemie D-8046 Garching WEST GERMANY Postfach 3640, 7500 Karlsruhe BRD/WEST GERMANY Dr. Holger Schultze Institut f. Angew. u. Anorg. Mr. Rolf Bohlander Chemie, Universitat Hamburg Kernforschgz. Karlsruhe, 1H Ch Martin-Luther-King-Platz 6 Postfach 3640 2000 Hamburg 43 W. GERMANY 75 Karlsruhe 1 WEST GERMANY Prof. Dr. H. Schumann Mr. Stefan Eggers Institut fur Anorganische und Institut fur Anorganische Analytische, Chemie der und Angewandte Chemie Technischen Universitat Berlin Universitat Hamburg Anorganische Chemie III Martin-Luther-King-Platz 6 Strasse des 17, June 135 2000 Hamburg 13 WEST GERMANY D-1000 Berlin 12 WEST GERMANY Prof. Dr. R. D. Fischer Mr. Udo Seemann Universitat Hamburg Institut fur Heisse Chemie Institut fur Anorganische und Kernforschungszentrum Karlsruhe Angewand~e Chemie Postfach 3640 Martin-Luther-King-Platz 6 7500 Karlsruhe 1 WEST GERMANY D-2000 Hamburg 13 WEST GERMANY Dr. K. H. den Haan Dr. E. Hahn Rijksuniversiteit Groningen Technische Universitat Berlin Nyenborgh 16 Strasse des 17 Juni 135 9747 AG Groningen 1000 Berlin 12 WEST GERMANY THE NETHERLANDS LIST OF PARTICIPANTS xi Dr. P. Pasman Dr. Maurizio Casarin Koninklijke/Shell Lab. Amsterdam National Council of Research PX-department Corso Stati Uniti Badhuisweg 3 c/o I.C.T.R. Amsterdam THE NETHERLANDS Padova ITALY Professor J. Teuben Prof. Enrico Ciliberto Laboratorium voor Anorganische Dipartimento di Chimica Scheikunde Universita di Catania Rijksuniversiteit Viale A. Doria 8 Nijenborgh 16 95125 Catania ITALY 9747 AG Groningen THE NETHERLANDS Prof. Ugo Croatto Dr. E. Benettolo Istituto di Chimica Generale Laboratorio di Chimica e Universita di Padova Tecnologia dei Radioelementi Via Loredan 4 del C.N.R., .Corso Stati Uniti 35100 Padova ITALY 35100 Padova ITALY Dr. Santo DiBella Prof. Gabriella Bombieri Dipartimento Chimica Dipartimento di Chimica Inorganica Universita di Catania Strutturistica Molecolare Viale A. Doria 8 Universita di Messina 95125 Catania ITALY Piazza Pugliatti 98100 Messina ITALY Professor I. Fragal~ Dipartimento di Chimica Dr. G. Bruno Universita di Catania Dipartimento di Chimica Viale A. Doria 6 Universita di Catania 95125 Catania ITALY Viale A. Doria 6 95125 Catania ITALY Dr. Antonino Gulino Dipartimento di Chimica Dr. Mario Bruzzone Universita di Catania Assoreni Viale A. Doria 8 Via Fabiani 95125 Catania ITALY 20097 S. Donato Milanese ITALY Prof. A. Mazzei Assoreni Dr. Adelio Canonico Via Fabiani ENEA 20097 San Donato Milanese Casella Postale N. 1 ITALY 75025 Policoro (Matera) ITALY Dr. Franco Ossola CNR-Rome Dr. Antonio Carbonaro ICTR- Area della Ricerca Assoreni Corso Stati Uniti Via Fabiani 35100 Padova ITALY 20097 San Donato Milanese ITALY
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