P-catenation

I 25 Targeting the Transcriptional Hub p-Caten/n Using Stapled Peptides... 

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 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... 

The pseudohalogen concept (p. 319) might lead one to expect the existence of a cyanate analogue of cyanogen but there is little evidence for NCO-OCN, consistent with the known reluctance of oxygen to catenate. By contrast. 

Catenation is well established in organotin chemistry and distannane derivatives can be prepared by standard methods (see Ge, p. 396). The compounds are more reactive than organodiger-manes e.g. Sn2Meg (mp 23°) inflames in air at its bp (182°) and absorbs oxygen slowly at room temperature to give (Me2Sn)20. Typical routes to higher polystannanes are ... 

Phosphorus (like C and S) exists in many allotropic modifications which reflect the variety of ways of achieving catenation. At least five crystalline polymorphs are known and there are also several amorphous or vitreous forms (see Fig. 12.3). All forms, however, melt to give the same liquid which consists of symmetrical P4 tetrahedral molecules, P-P 225 pm. The same molecular form exists in the gas phase (P-P 221pm), but at high temperatures (above 800°C) and low pressures P4 is in equilibrium with the diatomic form P=P (189.5 pm). At atmospheric pressure, dissociation of P4 into 2P2 reaches 50% at 1800°C and dissociation of P2 into 2P reaches 50% at 2800°. 

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). 

NaAs03 has an infinite polymeric chain anion similar to that in diopside (pp. 349, 529) but with a trimeric repeat unit LiAs03 is similar but with a dimeric repeat unit whereas /6-KASO3 appears to have a cyclic trimeric anion As309 which resembles the cyc/o-trimetaphosphates (p. 530). There is thus a certain structural similarity between arsenates and phosphates, though arsenic acid and the arsenates show less tendency to catenation (p. 526). The tetrahedral As 04) group also resembles PO4) in forming the central unit in several heteropoly acid anions (p. 1014). 

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. 

In these, As04 tetrahedra are built into the polyphosphate chains (309). Since the P—0—As bond has much the same sensitivity to hydrolysis as the As—0—As bond, they are rapidly hydrolyzed in aqueous solution to monoarsenate and mixtures of polyphosphates, the mean chain length of which depends on the As P ratio in the starting material (74)- Contrary to an idea based originally on gravimetric analysis (309), the As atoms are not distributed regularly in the chain, but statistically (308). The observation that, after careful hydrolysis, the phosphate content is exclusively in the form of polyphosphates provides chemical proof of catenation in the poly-arsenatophosphate anions. When arsenatophosphates with more than five P atoms per atom of As are hydrolyzed by hot water trimetaphosphates are formed, just as they are formed for all other high-molecular polyphosphates in solution (316). 

In recent years, dehydrocoupling reactions catalysed by early transition metal complexes have become an increasingly important method for generating catenated species of the p-block elements. In addition to producing cyclic oligomers, this approach is used to prepare linear oligomers and polymers such as polysilanes and polystannanes of the type H(MR2) H (M = Si, Sn) (see Section 10.1.4). ... 

Scheme 19. Synthesis of the poly[2]catenand 51b via demetalation of the poly[2]catenate 51a (i) 4-(dimethylamino)pyridine-p-toluenesulfonic acid 1 1 complex plus AT V -diisopro-pylcarbodiimide (ii) KCN, THF.

Catenated Organic Compounds of Silicon, Germanium, Tin, and Lead Henry Gilman, William H. Atwell, and Frank K. Cartledge Cyclobutadiene-Metal Complexes P. M. Maitlis Organoarsenic Chemistry W. R. Cullen... 

The catenation of nitrogen refers to the tendency of N atoms to be connected to each other, and is far lower than those of C and P. This is because the repulsion of lone pairs on adjacent N atoms weakens the N-N single bond, and the lone pairs can easily react with electrophilic species. The structures and examples of known compounds that contain chains and rings of N atoms are listed in Table 15.1.2. Note that none of these has a linear configuration of nitrogen atoms. 

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