Transition element chemistry

Electronegativities are of little value in transition element chemistry and no detailed tabulation need be given. A few useful points are in order, however. Across the 3d series, there is a steady increase, with a maximum of 1.75 at copper, falling slightly to 1.66 at zinc this arises from the larger radius of Zn, as discussed in Section 4.2, and it would be... 

Coordination and organometallic chemistry are often regarded as distinct tribal divisions in the discipline of inorganic chemistry. However, the historical reasons behind the distinction are no longer applicable the term coordination compound may have outlived its usefulness, and the term organometallic compound is often interpreted rather liberally. Accordingly, the two will be taken together as far as transition element chemistry is concerned. 

Octahedral six-coordination is especially favoured by the low-spin d6 configuration. This can be understood in terms of simple CFSE considerations. For M(III) (M = Co, Rh, Ir) and Pt(IV), hardly any complexes other than octahedral ones are known. These complexes are kinetically fairly inert, in the sense that they undergo ligand exchange reactions slowly. For this reason, much of our knowledge of kinetics and mechanism in transition element chemistry has come from studies of low-spin d6 octahedral complexes (see Sections 9.4 and 9.5). 

With the help of Raman spectroscopy many structural results have been obtained in the fascinating field of new cyclic sulfur molecules (Steudel, 1982). Out of the nearly immeasurable number of results in transition element chemistry, only two detailed studies shall be mentioned ... 

L. E. Orgel, An Introduction to Transition-Element Chemistry Ligand-Field Theory, Methuen, London, I960. Nonmathematical approach. 

C. Perrin - Octahedral Clusters in Transition Element Chemistry, J. of Alloys and Compounds 10, 262-263,1997 A. Perrin, M. Sergent - Rhenium Clusters in Inorganic Chemistry Structures and Metal-Metal Bonding, New J. Chem. 12,337, 1988 A. Perrin, C. Perrin, M. Sergent - Octahedral Clusters in Mo" and Re " Chalcohalide Chemistry, J. Less Common Met. 137,241,1988 ... 

As regards the transition elements, the first row in particular show some common characteristics which define a substantial part of their chemistry the elements of the lanthanide and actinide series show an even closer resemblance to each other. 

Some of the oxidation states given above, especially the higher oxidation states (7, 6) and oxidation state 0, are found only when the metal atom or ion has attached to it certain groups or ligands. Indeed the chemistry of the transition elements is so dominated by their tendency to form coordination complexes that this aspect of their behaviour must be considered in some detail. 

C. A. McAuliffe and W. Levason, Studies in Inorganic Chemistry, Vol. 1, Phosphine, Arsine and Stibine Complexes of the Transition Elements, Elsevier, Amsterdam, The Netherlands, 1979. 

Supplement to Mellor s Comprehensive Treatise on Inorganic and Theoretical Chemistry , Vol. V, Boron Part A, Boron-Oxygen Compounds , Longman, London, 1980, 825 pp. See also J. R. Bowser and T. P. Fehlner, Chap. 1 in H. W. Roesky (ed.). Rings, Clusters and Polymers of Main Group and Transition Elements, Elsevier, Amsterdam, 1989, pp. 1-48. 

Cluster and cage structures are widespread in the chemistry of main group elements, being particularly extensive in the case of boron (Chap. 6). For transition elements the principal... 

Because of the differing focus of interest in these elements their chemistries have not developed in parallel and the data on which strict comparisons might be based are not always available. Nevertheless many of the similarities and contrasts expected in the chemistry of transition elements are evident in this triad. The relative stabilities of different oxidation states in aqueous, acidic solutions are summarized in Table 24.2 and Fig. 24.1. 

F. P. Pruchnik, Organometallic Chemistry of the Transition Elements, Plenum Press, New York, 1990, 757 pp. 

The OrganometaUic chemistry of lanthanides is far less extensive than that of transition elements... 

In the preceding chapters we have studied the chemistry of the elements across the top of the periodic table and down the two sides. Now we shall consider the elements in the middle. These are usually referred to as the transition elements because chemists once believed that some elements behaved in a way intermediate between the extremes represented by the left and right... 

The most striking feature of the contrasts shown in Table 23-II is that the seventh-row elements display the multiplicity of oxidation states characteristic of transition elements rather than the drab chemistry of the +3 rare earth ions. Whereas Ce+3(aq) can be oxidized to Ce+4(aq) only with an extremely strong oxidizing agent, Th+Yaq) is the stable ion found in thorium salts and Th+3(aq) is unknown. In a similar... 

Some 20 years ago, I was privileged to share in writing a book on the descriptive chemistry of the 4d, 5d, 4f and 5f metals that included these eight elements within its compass (S.A. Cotton and F.A. Hart, The Heavy Transition Elements, Macmillan, 1975). This volume shares the same aim of covering the descriptive chemistry of silver, gold and the six platinum metals in some detail at a level suitable for advanced undergraduate and postgraduate study. 

General surveys of advances in coordination chemistry appear in Annual Reports , The Royal Society of Chemistry, London, Section A. More specialized reports were published in the form of the Specialist Periodical Reports Inorganic Chemistry of the Transition Elements , The Chemical Society, London (Volumes 1-6), which reviewed the literature published between 1971 and 1976, and the Specialist Periodical Reports Inorganic Chemistry of the Main Group Elements , The Chemical Society, London (Volumes 1-5), which reviewed the literature published between 1971 and 1976. Both these series have now been discontinued. 

Annual reviews of both transition element and main group chemistry are now published periodically in Coord. Chem. Rev. and the details of those which have appeared to date are given below. 

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