PART I I

I N 0 RG AN I C C H EM I ST RY

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9 Introduction

By D. W. A. SHARP Department of Chemistry, University of Glasgow, Glasgow G 72 800

The general form of the 1974 Annual Reports (Vol. 71) on Inorganic Chemistry follows that of Volume 70 with the coverage of series of related complexes of transition elements and of properties that relate mainly to the ligand in a separate section rather than separately under each element. In Annual Reports specific note is taken of the existence of the Specialist Periodical Reports series, and there- fore we do not attempt to provide a comprehensive coverage but rather to point out those aspects of inorganic chemistry which the Reporter feels are of particular significance. In particular, we do not cover physical measurements on inorganic compounds unless these lead to significant advances in our under- standing of the structure or the bonding of the compound.

Because of the necessity to keep down the length of articles in this year’s Report there has been a more conscious attempt to reduce the repetition of material between the various sections of the Report. This could mean that readers will need to consult sections other than those that they would normally use but we hope that in so doing they will find yet other information of use. Of necessity we generally exclude references to full reports when preliminary communications have already been mentioned in a previous volume of Annual Reports. We have cut down drastically on making references to review articles although a limited number of more general reviews on inorganic topics are listed in this introduction.

Once again it is difficult to pick out areas of development for special mention but very significant advances continue to be made in the chemistry of the inter- action of olefins and polyolefins with metals, and in the incorporation of metals and other heteroatoms into the cage structures of boranes and particularly of carbaboranes. One of the most interesting isolated observations is that Na- may be present in the product of the reaction between sodium metal and a cyclic polyaminoether (p. 172). It tends to be forgotten that addition of an electron to a gaseous atom is an exothermic process for most elements. Equally interesting is evidence for NaF, and NaCl, in the gas phase (p. 244).

Volume XV of Inorganic Syntheses is devoted principally to transition-metal compounds (including olefin, dinitrogen, triphenylphosphine complexes) al- though there are sections on phosphorus compounds and germanium hydride

169

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170 D. W . A . Sharp

derivatives.’ Volumes of Gmelin published during the year include coverage of oxygen (System number 3), transuranium elements (7), boron (13), carbon and organoiron derivatives (14), silicon (1 9, organonickel derivatives (17), lanthan- ides (39), tin (46), and silver (61). Amongst the more important books which have become available in 1974 should be mentioned volumes of thermodynamic data on inorganic chalcogenides,2 selenium and te l l~r ium,~ the actinides: rare-earth inter metallic^,^ phosphine, arsine, and stibine comple~es,~ iron-sulphur pro- teins,’ organotransition-metal chemistry,’ and catalysis by metal cornplexe~.~

Amonst the more important general articles and reviews that have been published in 1974 are a revision of the M4+ effective ionic radii,” reviews of the chemistry of the metallic elements in the ionosphere and mesosphere,’’ hydrogen bonding in solids,’ ABX, compound^,'^ the marcasite structure,” U.V. and X-ray photoelectron spectroscopy,’6 the effects of high pressure on the chemistry and spectra of inorganic compound^,'^ metalloboranes,’ metalloboroxanes,’9 various aspects of silicon chemistry,20 metalloenzymes,2 the relaxation of excited states of

fluoride complexes in aqueous solution,’

G. W. Parshall (Editor), Inorg. Synth., 1974, XV. ’ K. C. Mills, ‘Thermodynamic Data for Inorganic Sulphides, Selenides, and Tellurides’, Butterworths, London, 1973. A. A. Kudryavtsev, ‘Chemistry and Technology of Selenium and Tellurium’, Colletts, London, 1974. A. J. Freeman and J. B. Darby, ‘The Actinides’, Vols. 1 and 2, Academic Press, New York, 1974. W. E. Wallace, ‘Rare Earth Intermetallics’, Academic Press, New York, 1973. C. A. McAuliffe, ‘Transition Metal Complexes of Phosphorus, Arsenic, and Antimony Ligands’, MacMillan, London, 1973. W. Lovenborg, ‘Iron-Sulphur Proteins’, Vols. 1 and 2, Academic Press, New York, 1974.

a R. F. Heck, ‘Organotransition Metal Chemistry’, Academic Press, New York, 1974; P. W. Jolly and G. Wilke, ‘The Organic Chemistry of Nickel’, Academic Press, New York, 1974. M. M. Taqui Khan and A. E. Martell, ‘Homogeneous Catalysis by Metal Complexes’, Vols. I and 11, Academic Press, New York, 1974; P. N. Rylander, ‘Organic Syntheses with Noble Metal Catalysts’, Academic Press, New York, 1974.

T. L. Brown, Chem. Rev., 1973, 73, 645. l o 0. Knop and J. S . Carlow, Canad. J . Chem., 1974,52,2175.

l 2 A. Novak, Structure and Bonding, 1974, 18, 177. l 3 G. Hefter, Co-ordination Chem. Rev., 1974, 12, 221. l 4 J. F. Ackerman, G . M. Cole, and S . L. Holt, Inorg. Chim. Acra, 1974, 8, 323.

I 6 W. L. Jolly, Co-ordination Chem. Rev., 1974, 13, 47; R. L. de Kock and D. R. Lloyd,

l 7 E. Sinn, Co-ordination Chem. Rev., 1974, 12, 185; H. G. Drickamer, Angew. Chem.

l a N. N. Greenwood and I. M. Ward, Chem. SOC. Rev., 1974, 3, 231. l 9 S. K. Mehrotra, G. Srivastava, and R. C. Mehrotra, J. Organometallic Chem., 1974,

* O H. Burger, R. Eujen, G. Fritz, F. Hofler, and E. Hengge, Topics in Current Chem., 1974,

’ I U. Weser, R. R. Crichton, M. Llinas, and F. L. Siegel, Structure and Bonding, 1973, 17.

A. Kjekshus and T. Rakke, Structure and Bonding, 1974, 19, 85.

Adv. Inorg. Chem. Radiochem., 1974, 16, 66.

Internat. Edn., 1974, 13, 39.

73, 277.

Vols. 50 and 5 1.

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Introduction 171

transition-metal complexes,22 transition-metal complexes in cancer chemo- therapy,23 ligand effects on the kinetics of substitution and redox reactions,24 acid-catalysed reactions of transition-metal complexe~,~ perchlorate complexes,26 (CF,),N fluorinated peroxides,28 fluoros~lphates,~~ metal nitro- ~ y l s , ~ ' transition-metal oxime derivative^,^' tripodal amine cornplexe~,~~ metalloprotein redox reactions,33 vitamin B, systems,34 and cyanide phosphine complexes.35

2 2 M. K. De Armond, Accounts Chem. Res., 1974, 7 , 309. 2 ' M. J. Cleare, Co-ordination Chem. Rev., 1974, 12, 349. 2 4 V. Gutmann and R. Schmid, Co-ordination Chem. Rev., 1974, 12, 263. 2 5 P. J. Staples, Co-ordination Chem. Rev., 1973, 11, 277. 2 6 L. Johansson, Co-ordination Chem. Rev., 1974, 12, 241. :: H. G. Ang and Y. C. Syn, Adv. Inorg. Chem. Radiochem., 1974, 16, 1.

2 9 A. W. Jache, Adv. Znorg. Chem. Radiochem., 1974, 16, 177. 30 J. H. Enemark and R. D. Feltham, Co-ordination Chem. Rev., 1974, 13, 539. 3 1 A. Chakravorty, Co-ordination Chem. Rev., 1974, 13, 1. 3 2 S. G. Zipp, A. P. Zipp, and S . K. Madan, Co-ordination Chem. Rev., 1974, 14, 29. 3 3 L. E. Bennett, Progr. Inorg. Chem., 1973, 18, 1. 3 4 D. G. Brown, Progr. Inorg. Chem., 1973, 18, 177. 3s P. Rig0 and A. Turco, Co-ordination Chem. Rev., 1974, 13, 133.

R. A. De Marco and J. M. Shreeve, Adv. Znorg. Chem. Radiochem., 1974, 16, 110.

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