Adoances in Physical Organic Chemistry This Page Intentionaiiy Left Blank . Advances zn Physical Organic Chemistry Edited by V. GOLD Department of Chemistry King’s College, University of London VOLUME 10 1973 Academic Press, London and New York A subsidiary of Hnrcourt Brace Jovunovich, Publishers BCADEMIC PRESS INC. (LONDON) LTD 24-28 Oval Road, London NW1 U.S. Edition pubtished by ACADEMIC PRESS INC. 111 Fifth Avenue, New York, New York 10003 Copyright 01973 By Academic Press Inc. (London) Ltd All Rights Reserved No part of this book may be reproduced in any form by photostat, microfilm, or any other means, without written permission from the publishers Library of Congress Catalog Card Number: 62-22125 ISBN 0-12-033510-7 PRINTED I N GREAT BRITAIN BY WILJXAM CLOWES 85 SONS LIMITED LONDON, COLCRESTER AND BECCLES CONTRIBUTORS TO VOLUME 10 D. BETHELL, The Robert Robinson Laboratories, University of Liverpool, Liverpool, England. M. R. BRINKMAN, The Robert Robinson Laboratories, University of Liverpool, Liverpool, England. P. W. CABELL-WHITING, Department of Organic Chemistry, The University, Zernikelaan, Groningen, The Netherlands. R. E. CARTER,Organic Chemistry 2, Lund Institute of Technology, Chemical Center, S-220 07 Lund 7, Sweden. M. FLEISCHMANN, Departm,ent of Chemistry, Th,e University,Southampton SO9 5 N H , England. H. HOGEVEEN,Department of Organic Chemistry, The University, Zernikelaan, Groningen, The Netherlands. L. MELANDER,Department of Organic Chemistry, University of Goteborg and Chalmers Institute of Technology, S-402 20 Goteborg 5, Sweden. D. PLETCHER, Department of Chemistry, The University, Southampton SO9 5 N H , England. This Page Intentionaiiy Left Blank CONTENTS CONTRIBIJTORS TO VOLUME 10 . v Experiments on the Nature of Steric Isotope Effects EOBERT E. CARTERand LARSMELANDER I . Introduction . 11. Theory . A. Bartell’s Perturbation Treatment . B. An Alternative, Somewhat Naive and Unsatisfactory Model . 111. Survey of Experimental Results . References . 1 5 5 10 14 26 The Reactivity of Carbonium Ions Towards Carbon Monoxide H. HOGEVEEN I. Introduction . . 11. Reactivity and Stabilization of Tertiary Alkyl Cations 111. Reactivity and Stabilization of Secondary Alkyl Cations . A. Interconversion of Tertiary and Secondary Pentyloxocarbonium Ions . B. Rate Expressions for the Rearrangement-Carbonylation C. Interconversion of Tertiary and Secondary Butyloxocarbonium Ions . D. Kinetic and Therinodynamic Control in the Reversible Carbonylation of the 2-Norbornyl Cation . . IV. Interception of Unstable Cations by Carbon Monoxide A. Primary Alkyl Cations . B . Vinyl Cations V. Reactivity of Stabilized Carbonium Ions . VI. Some Remarks on the Mechanism of Carbonylation . VII. Conclusions References . vii 29 31 34 34 37 40 41 43 43 45 46 50 51 51 viii CONTENTS Chemically Induced Dynamic Nuclear Spin Polarization and its Applications D. BETHELL and M. R. BRINKMAN I. Introduction . A. Scope . B. TheN.M.R. Experiment . C. Dynamic Nuclear Polarization . 11. The Radical Pair Theory of CIDNP . . A. BasicConcepts B. The Relative Energies of Ground-State T and S Mani. folds of a Radical Pair C. The Dynamic Behaviour of Radical Pairs . D. Mechanisms of T-S Mixing . E. Quantitative Aspects of To-S Mixing . 111. Qualitative Analysis of CIDNP Spectra . . IV. CIDNP at Low Magnetic Fields V. Applications of CIDNP A. Scope and Limitations . B. Reactions of Diacyl Peroxides and Related Compounds . C. Reactions of Azo-, Diazo-, and Related Compounds . D. The Photolysis of Aldehydes and Ketones . E. Reactions Involving Organometallic Compounds . F. Ylid and Related Molecular Re