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A Specialist Periodical Report Organophosphorus Chemistry Volume 8 A Review of the Literature published between July 1975 and June 1976 Senior Reporter S. Trippett, Department of Chemistry, University of Leicester Reporters D. W. Allen, Shefield Polytechnic R. S. Davidson, University of Leicester R. S. Edmundson, University of Bradford J. B. Hobbs, Max Planck lnstitut fiir Experimenfelle Medizin, Gottingen, W, Germany D. W. Hutchinson, University of Warwick R. Keat, University of Glasgow J. A. Miller, University of Dundee D. J. H. Smith, University of Leicester J. C. T e b by, North Stafordshire Polytechnic, Stoke-on- Trent B. J. Walker, Queen’s University of Belfast 0 Copyright 1977 The Chemical Society Burlington House, London, WIV OBN ISBN : 0 85186 076 1 ISSN : 0306-0713 Library of Congress Catalog Card No. 73-268317 Printed in Great Britain by Adlard & Son, Ltd. Bartholornew Press, Dorking Foreword The volume of published work in organophosphorus chemistry has again increased, and several Reporters have had great difficulty in keeping within their allotted space. Much, but not all, of the research has been of a routine and predictable nature. The stimulus provided by the discovery of phosphonomycin is still being felt. It would be interesting to know just how many research projects and proposals have been linked, however tenuously, to this phosphorus-containing antibiotic. Six-co-ordinate species are being identified more frequentIy. Some are remarkably stable and have been isolated, whereas the intermediacy of others in reactions has been inferred from kinetic data. Clearly, much more will be heard of these. Finally, on the instrumental front, Fourier-transform 31Pn.m.r. spectroscopy is proving to be a very powerful tool for the detection and study of unstable intermediates, for example in Arbusov reactions, and one can look forward to the solution of many long-standing problems in organophosphorus chemistry using this technique. We hope to report on some of these in Volume 9. S.Trippett Contents Chapter 1 Phosphines and Phosphonium Salts By D, W. Allen 1 1 Phosphines Preparation From Halogenophosphine and Organometallic Reagents From Metallated Phosphines By Addition of P-H to Unsaturated Compounds By Reduction Miscellaneous Reactions Nucleophilic Attack at Carbon Carbonyls Miscellaneous Nucleophilic Attack at Halogen Nucleophilic Attack at Other Atoms Miscellaneous 1 1 1 2 5 6 8 10 2 Phosphonium Salts Preparation Reactions Alkaline Hydrolysis Additions to Vinylphosphonium Salts Miscellaneous 18 18 21 21 23 25 3 Phospholes 27 4 Phosphorins 29 Chapter 2 Quinquecovalent Phosphorus Compounds By S. Trippetf 10 10 11 12 15 17 31 1 Introduction 31 2 Structure and Bonding 32 3 Acyclic Systems 33 vi Contents 4 Four-membered Rings 35 5 Five-membered Rings Phospholens 1,2-Oxaphospholans 1,3,2-Dioxaphospholans 1,3,2-Dioxaphospholens 1,3,2-Oxazaphospholidines Miscellaneous 36 36 37 37 39 41 44 6 Six-membered Rings 46 7 Six-co-ordinate Species 46 Chapter 3 Halogenophosphines and Related Compounds By J. A. Miller 50 1 Halogenophosphines Physical and Structural Aspects Preparation Reactions with Simple Alkenes and Aromatic Compounds Reactions in which Phosphorus is Electrophilic Biphilic Reactions Miscellaneous Reactions Silyl- and Related Phosphines 50 50 51 52 53 54 58 59 2 Halogenophosphoranes Physical and Structural Aspects Preparation of Phosphoranes from Phosphorus(rI1) Compounds Preparation of Phosphoranes by Exchange Methods Reactions of Phosphoran