Catenation Group 15 elements

The hydrides of the later main-group elements present few problems of classification and are best discussed during the detailed treatment of the individual elements. Many of these hydrides are covalent, molecular species, though association via H bonding sometimes occurs, as already noted (p. 53). Catenation flourishes in Group 14 and the complexities of the boron hydrides merit special attention (p. 151). The hydrides of aluminium, gallium, zinc (and beryllium) tend to be more extensively associated via M-H-M bonds, but their characterization and detailed structural elucidation has proved extremely difficult. 

The types of molecules considered in this work are those that have structural or chemical features that are manifestly different than are those of their more common oxidation state counterparts. Because of the breadth of this subject, selected examples are presented to illustrate typical behavior. The properties of the types of compounds containing the elements in more typical oxidation states may be found in the Inorganic and Organometallic sections describing each element or gronp and will not be discussed in this article. Similarly, minerals, metal phosphides, metal carbides, and compounds where the oxidation state of the element is low based on formal electron counting techniques (as in some catenated Catenation group 14 compounds), but that do not result in unusual chemistry, are not included. 

Transition metal phosphinidene complexes were originally prepared in order to access what was expected to be a rich chemistry of phosphorus(I)T However, terminal phosphinidenes have been found to be difficult to prepare, partly because they tend to either catenate or bridge. This is a manifestation of the double-bond rule for the main group elements. However, breakthroughs in syntheses of these complexes came about through the use of devious synthetic techniques in combination with sterically encumbered ligands. 

Ishikawa, M., Kumada, M., Photolysis of Organic Derivatives of Catenated Group IVB Elements, Rev. Silicon Germanium Tin Lead Compounds 4 [1979] 7/58. 

H.G. Von Schnering, Catenation of P atoms, in Heteroatomic Rings, Chains and Macromolecules of Main Group Elements, Elsevier, Amsterdam, 1977. 

All Group IV elements form tetrachlorides, MX4, which are predominantly tetrahedral and covalent. Germanium, tin and lead also form dichlorides, these becoming increasingly ionic in character as the atomic weight of the Group IV element increases and the element becomes more metallic. Carbon and silicon form catenated halides which have properties similar to their tetrahalides. 

The ability of C to catenate (i.e. to form bonds to itself in compounds) is nowhere better illustrated than in the compounds it forms with H. Hydrocarbons occur in great variety in petroleum deposits and elsewhere, and form various homologous series in which the C atoms are linked into chains, branched chains and rings. The study of these compounds and their derivatives forms the subject of organic chemistry and is fully discussed in the many textbooks and treatises on that subject. The matter is further considered on p. 374 in relation to the much smaller ability of other Group 14 elements to form such catenated compounds. Methane, CH4, is the archetype of tetrahedral coordination in molecular compounds some of its properties are listed in Table 8.4 where they are compared with those of the... 

Some of the alkali metal-group 15 element systems give compounds of stoichiometry ME. Of these, LiBi and NaBi have typical alloy stmc-tures and are superconductors below 2.47 K and 2.22 K respectively. Others, like LiAs, NaSb and KSb, have parallel infinite spirals of As or Sb atoms, and it is tempting to formulate them as M+ (E )" in which the (E )" spirals are iso-electronic with those of covalently catenated Se and Te (p. 752) however, their metallic lustre and electrical conductivity indicate at least some metallic bonding. Within the spiral chains As-As is 246 pm (cf. 252 pm in the element) and Sb-Sb is 285 pm (cf. 291 pm in the element). 

Catenated Organic Compounds of the Group IV Elements, 4,1 Conjugate Addition of Grignard Reagents to Aromatic Systems, 1, 221 Cyclobutadiene Metal Complexes, 4, 95 Cyclopentadienyl Metal Compounds, 2, 365 Diene-Iron Carbonyl Complexes, 1, 1... 

In the right part of the Table hydrides having covalent characteristics are observed. For the elements of the last groups several covalent hydrogen compounds are known numerous compounds are given by B, C, Si, Ge, N, P, O, S, Se. In the usual ambient conditions, as it is well-known, the carbon chemistry is especially rich of hydrides (that is of several series of hydrocarbons). In this class of compounds more or less complex molecules and structures are found the catenation (chainforming) tendency is a characteristic shown by several elements in this portion of the Periodic Table. 

Condensation polymerization, in which some very stable molecule XZ is eliminated from equimolar amounts of species RXE—X and RXE—Z (E being the element that catenates and R some side group), is more widely applicable ... 

Arsenic forms a large number of compounds with other Group 5 members. These are dealt with element by element down the group. However, in the case of arsenic only its catenated and jr-bonded compounds are dealt with. 

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