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The present volume on organomolybdenum chemistry completes the description of the rich chemistry of the 15-electron fragment 5LMo(CO)2. The 5L ligands are ring systems and represent mainly C5H5, indenyl, and C5(CH3)5 or several other substituted derivatives of C5H5. The first sections describe the bonding of this fragment to other 1L systems which formally contribute one electron in the form of alkyl and aryl groups or various side-on bonded E=CR2 derivatives, two electrons in the form of carbene, isonitril, or ylide ligands, and even three electrons in the form of carbyne ligands, resulting in a formal molybdenum-to-carbon triple bond represented by the general formula 5LMo(CO)2hCR. Three other sections deal with the bonding of this fragment to 2L ligands (mainly olefines). 3L ligands (allyl, trimethylenemethane derivatives), and 4L ligands (derivatives of butadiene). Various neutral two-electron donors, halogens or other -bonded heteroatoms, and charges satisfy the electron requirement of the compounds in obeing the Effective Atomic Number rule. In compounds with four different types of ligands and with a cis arrangement of the two CO groups, metal chirality appears. These options generate versatile types of compounds and isomers, thus stimulating further research in this area. An empirical formula index and ligand index at the end facilitate the compound search.
to thank Messrs J. R. Sanders, W. E. Lindsell and M. G. Swanwick for helping to check the text and references and prepare indexes. Finally, I should like to thank my wife for the very considerable assis tance she has given me in the writing and production of this book. M. L. H. G. Contents Preface to the Third Edition, Volume Two Page v INTRODUCTION TO VOLUME TWO I Oassification I The IS-electron rule 2 (i) The basis of the I8-electron rule p. 4, (ii) Exceptions to the I8-electron rule p. 5 1. TWO-ELECTRON LIGANDS 7 A. Classification 7 B. The preparation of olefin-transition metal complexes 7 (a) Displacement of solvent ligands p. 9, (b) Preparations from metal carbonyls p. 9, (c) Less common preparative routes p. 11, Reductive olefination method p. 12 C. A molecular orbital description of the bonding in orga- metallic complexes 13 (a) General comments p. 13, (b) Symmetry considerations p. 13, (c) Energies of the molecular orbitals p. 14 D. A description of the bonding of 2-electron ligands to transition metals 14 E. General comments of 2-electron ligands 19 (a) Infrared studies p. 20, (b) Effect of olefin substituents p. 21, (c) The rotation of ethylene about the ligand-metal bond p. 22, (d) Chemical properties p. 23 F. Particular complexes of metals with 2-electron ligands 25 (a) Copper, silver and gold p. 25, Complexes with benzene p. 28, (b) Nickel, palladium and platinum p.
to thank Messrs J. R. Sanders, W. E. Lindsell and M. G. Swanwick for helping to check the text and references and prepare indexes. Finally, I should like to thank my wife for the very considerable assis tance she has given me in the writing and production of this book. M. L. H. G. Contents Preface to the Third Edition, Volume Two Page v INTRODUCTION TO VOLUME TWO I Oassification I The IS-electron rule 2 (i) The basis of the I8-electron rule p. 4, (ii) Exceptions to the I8-electron rule p. 5 1. TWO-ELECTRON LIGANDS 7 A. Classification 7 B. The preparation of olefin-transition metal complexes 7 (a) Displacement of solvent ligands p. 9, (b) Preparations from metal carbonyls p. 9, (c) Less common preparative routes p. 11, Reductive olefination method p. 12 C. A molecular orbital description of the bonding in orga- metallic complexes 13 (a) General comments p. 13, (b) Symmetry considerations p. 13, (c) Energies of the molecular orbitals p. 14 D. A description of the bonding of 2-electron ligands to transition metals 14 E. General comments of 2-electron ligands 19 (a) Infrared studies p. 20, (b) Effect of olefin substituents p. 21, (c) The rotation of ethylene about the ligand-metal bond p. 22, (d) Chemical properties p. 23 F. Particular complexes of metals with 2-electron ligands 25 (a) Copper, silver and gold p. 25, Complexes with benzene p. 28, (b) Nickel, palladium and platinum p.