Block to Group 13 Metal Bonds

Attempts to classify carbides according to structure or bond type meet the same difficulties as were encountered with hydrides (p. 64) and borides (p. 145) and for the same reasons. The general trends in properties of the three groups of compounds are, however, broadly similar, being most polar (ionic) for the electropositive metals, most covalent (molecular) for the electronegative non-metals and somewhat complex (interstitial) for the elements in the centre of the d block. There are also several elements with poorly characterized, unstable, or non-existent carbides, namely the later transition elements (Groups 11 and 12), the platinum metals, and the post transition-metal elements in Group 13. 

The term Zintl phase is applied to solids formed between either an alkali- or alkaline-earth metal and a main group p-block element from group 14, 15, or 16 in the periodic table. These phases are characterized by a network of homonuclear or heteronuclear polyatomic clusters (the Zintl ions), which carry a net negative charge, and that are neutralized by cations. Broader definitions of the Zintl phase are sometimes used. Group 13 elements have been included with the Zintl anions and an electropositive rare-earth element or transition element with a filled d shell (e.g. Cu) or empty d shell (e.g. Ti) has replaced the alkali- or alkaline-earth element in some reports. Although the bonding between the Zintl ions and the cations in the Zintl phases is markedly polar, by our earlier definition those compounds formed between the alkali- or alkaline-earth metals with the heavier anions (i.e. Sn, Pb, Bi) can be considered intermetallic phases. 

The values may be understood in terms of the cohesive forces operating in the various cases. The basis of the theory is that which is presented in Section 4.3 in the discussion of the atomic volume curve. The forces range from metallic bonding in Groups 1 to 12/13, followed by covalent bonding in the p-block non-metallic elements, to van der Waals forces (London interatomic forces) which operate alone in the Group 18 elements. 

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