M. Gerloch, E.G. Constable Transition Metal Chemistry VCH Transition Metal Chemistry. M. Gerloch, E. C. Constable Copyright © 1994 VCH Verlagsgesellschaft mbH, Weinheim ISBN: 3-527-29218-7 © VCH Verlagsgesellschaft mbH, D-69451 Weinheim (Federal Republic of Germany), 1994 Distribution: VCH, P.O. Box 101161, D-69451 Weinheim, Federal Republic of Germany Switzerland: VCH, P.O. Box, CH-4020 Basel, Switzerland United Kingdom and Ireland: VCH, 8 Wellington Court, Cambridge CBl IHZ, United Kingdom USA and Canada: VCH, 220 East 23rd Street, New York, NY 10010-4606, USA Japan: VCH, Eikow Building, 10-9 Hongo 1-chome, Bunkyo-ku, Tokyo 113, Japan ISBN 3-527-29218-7 (VCH, Weinheim) ISBN 1-56081-885-9 (VCH, New York) Malcolm Gerloch, Edwin C. Constable Transition Metal Chemistry The Valence Shell in d-Block Chemistry Weinheim · New York Basel · Cambridge · Tokyo Dr. Malcolm Gerloch University Chemistry Laboratory Lensfield Road Cambridge CB2 IEW United Kingdom Prof. Dr. Edwin C. Constable Institut fur Anorganische Chemie Universitat Basel Spitalstr. 51 CH-4056 Basel Switzerland This book was carefully produced. Nevertheless, authors and publisher do not warrant the information contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Published jointly by VCH Verlagsgesellschaft, Weinheim (Federal Republic of Germany) VCH Publishers, New York, NY (USA) Editorial Director: Dr. Thomas Mager Production Manager: Elke Littmann Library of Congress Card No. applied for. A catalogue record for this book is available from the British Library. Die Deutsche Bibliothek - CIP-Einheitsaufnahme: Gerloch, Malcolm: Transition metal chemistry: the valence shell in d-block chemistry / Malcolm Gerloch; Edwin C. Constable. - Weinheim; New York; Basel; Cambridge; Tokyo: VCH, 1994 ISBN 3-527-29219-5 (Weinheim ) brosch. ISBN 3-527-29218-7 (Weinheim ) Gb. ISBN 1-56081-884-0 (New York) NE: Constable, Edwin C.: © VCH Verlagsgesellschaft mbH, D-69451 Weinheim (Federal Republic of Germany), 1994 Printed on acid-free and chlorine free paper All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form - by photoprinting, microfilm, or any other means - nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Composition: Hagedornsatz GmbH, D-68519 Viernheim. Printing: betz-druck gmbh, D-64291 Darmstadt. Bookbinding: Industrie- und Verlagsbuchbinderei Heppenheim GmbH, D-64630 Heppenheim. Printed in the Federal Republic of Germany To our wives, Gwynneth Neal-Freeman and Catherine Housecraft, for their love, patience, hard work and cajolary. Also to Satin, Index, Philby and Isis [...]... coordinate to a metal ion in more than one way This is described as ambidentate behaviour In such cases, we commonly indicate 6 1 An Introduction to Transition- Metal Chemistry Table 1-3 Some typical monodentate ligands and representative complexes that they form Monodentate ligands Donor atom Example o 2- O [MnO4] - Halides, F-, ΟΓ, Br-, I- F, Cl, Br, I [NiCl4] 2-, [CrF6] 3- H- H [ReH9] 2- NCS- Nor S [Cr(NH3M^CS)]2+... Properties of Transition- Metal Compounds Finally, we summarize some of the properties of transition- metal compounds and attempt to distinguish those which are characteristic of a transition- metal complex as opposed to any metal complex Variable oxidation state - One obvious feature of transition- metal chemistry is the occurrence of a number of characteristic oxidation states for a particular metal 18 1... both main group and transition- metal ions Transition- metal complexes may gain or lose ligands to change geometry and so do main group complexes The existence of coordination chemistry in the transition- metal block does not set these metals apart from those of the main groups Suggestions for further reading 1 F Basolo, R.C Johnson, Coordination Chemistry, 2nd ed., Science Reviews - This is an easy to... glycinato, O- gty H 2 NCH 2 CH 2 NH 2 1 ,2-diaminoethane, ethylenediamine, en Ph2PCH2CH2PPh2 bis(diphenylphosphino)-ethane, dppe P,P' [Fe(dppe)2(CO)] -S515^AsMe2 Ij J Il I l,2-bis(dimethylarsino)ΙΛΑΙΊΤΑΓΙΑ Hiorc As 9 As' [CrCl4(diars)]~ AsMe2 Ph Ph [Re(S2C2Ph2)3] \ !,I'-bipyridine, ff 2,2f-dipyridyl, bipy.bpy 1,10-phenanthroline, N,N' N >N' [Mn(bpy)3]2+ [Ru(phen)3]2 8 1 An Introduction to Transition- Metal Chemistry. .. Inorganic Chemistry, Harper Collins, New York, 1993 - An excellent general introduction to inorganic chemistry, with first rate chapters dealing with transition metal chemistry 3 RA Cotton, G Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley, New York, 1989 - A relatively comprehensive work with a great deal of descriptive material concerned with transition metal chemistry 4 A.G Sharpe, Inorganic Chemistry, ... lanthanum to mercury) The term 'transition' arises from the elements' supposed transitional positions between the metallic elements of groups 1 and 2 and the predominantly non-metallic elements of groups 13 to 18 Nevertheless, the transition elements are also, and interchangeably, known as the transition metals in view of their typical metallic properties The chemistry of the transition elements has been... ft ^i S > ^ w OJ C>J « > ^ OJ VD « OO 3 HH ^ α R-SS Π) ο 53 > ^ S I ε: 5 VO OO S - Ζ Ο Uj ϊ S-I NJ S k4 κ> 1- I § S 2 ή ^ 8 ^ OO ^J 0 0 £ S ί5 >^> ^ - < „ » σ< ^g ^ OO 5; O K) NJ K) " i ff 5 t M Λ δ I S-£ 8 H ΟΛ *ϊ ^o i** σν O K) νο g E % ε s ^ I2 i U) e S κ> -^ S g H οο ·*· *: N> K) l_k » N ^ ) U -J O ε s » I |-> f t ^ l a 1 - NJ K) S SL Π ^ S I s S- B S — — * S OO Λ G 3 < οο ^ G ϊ O UJ P ιH UJ... £ ? § £ 2 S *5 S OO OO j-j VO οο Ξ O °° ε S =ι 1 -~ j KJ OO 2 ^Cj *^> QO * ο OO ^* * *^ * ^ 53 ^ 5 N !S β " tU Ν> W I, S ** α S M ^ &5 ? ift A U K) a » S K M H ff ^1 g S § fsj ο ^5 νο « Β" g * 2 1 K) £ -J ^ 2 S >> * ^o B & % Λ « 'ο ON UJ " 'S ξ K^ UJ "^ 9 i M5 uj M OO ^ s S «—· NJ = ϊδ £ > e S *ι 1 1ή 1 % I* -J - u> K) fo g ON -^ Λ Ό S ^o ι S J^W J ^W ^ - - ^ < - Wl > ^ Gd . Building, 1 0-9 Hongo 1-chome, Bunkyo-ku, Tokyo 113, Japan ISBN 3-5 2 7-2 921 8-7 (VCH, Weinheim) ISBN 1-5 608 1-8 8 5-9 (VCH, New York) Malcolm Gerloch, Edwin C. Constable Transition Metal Chemistry The . listed, in Transition Metal Chemistry. M. Gerloch, E. C. Constable Copyright © 1994 VCH Verlagsgesellschaft mbH, Weinheim ISBN: 3-5 2 7-2 921 8-7 2 1 An Introduction to Transition- Metal Chemistry Table . ligands o 2 - Halides, F-, ΟΓ, Br-, I- H- NCS- Donor atom O F, Cl, Br, I H Nor S Example [MnO 4 ] - [NiCl 4 ] 2 -, [CrF 6 ] 3 - [ReH 9 ] 2 - [Cr(NH 3 M^CS)] 2 + [Cr(NH 3 ) 5 (NCS)] 2+ NO 2 -