Covalent hydrides of boron

A non-metal or weakly electropositive metal X in Group III of the periodic table would be expeeted to form a covalent volatile hydride XHj. In fact, the simplest hydride of boron is BjHf, and aluminium hydride is a polymer (AlHj) . 

The element before carbon in Period 2, boron, has one electron less than carbon, and forms many covalent compounds of type BX3 where X is a monovalent atom or group. In these, the boron uses three sp hybrid orbitals to form three trigonal planar bonds, like carbon in ethene, but the unhybridised 2p orbital is vacant, i.e. it contains no electrons. In the nitrogen atom (one more electron than carbon) one orbital must contain two electrons—the lone pair hence sp hybridisation will give four tetrahedral orbitals, one containing this lone pair. Oxygen similarly hybridised will have two orbitals occupied by lone pairs, and fluorine, three. Hence the hydrides of the elements from carbon to fluorine have the structures... 

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. 

Boron and hydrogen form many compounds and they exhibit unusual structural forms. Several of the boranes are listed in Table 13.2. Covalent hydrides are generally compounds that have low boiling points. Consequently, they are often referred to as volatile hydrides. 

Boron s chemistry is so different from that of the other elements in this group that it deserves separate discussion. Chemically, boron is a nonmetal in its tendency to form covalent bonds, it shares more similarities with carbon and silicon than with aluminum and the other Group 13 elements. Like carbon, boron forms many hydrides like silicon, it forms oxygen-containing minerals with complex structures (borates). Compounds of boron have been used since ancient times in the preparation of glazes and borosilicate glasses, but the element itself has proven extremely difficult to purify. The pure element has a wide diversity of allotropes (different forms of the pure element), many of which are based on the icosahedral Bj2 unit. 

In covalent hydrides, hydrogen and the metal are linked by a covalent bond. Aluminum, silicon, germaninm, arsenic, and tin are some of the metals whose covalent hydride structures have been stndied extensively. Some ionic hydrides, snch as LiH or MgH2, exhibit partial covalent character. The complex hydrides, such as lithium aluminum hydride and sodium borohydride, contain two different metal atoms, usually an alkali metal cation bound to a complex hydrido anion. The general formula for these compounds is M(M H4) , where the tetrahedral M H4 contains a group IIIA metal such as boron. 

Because boron has a small atom and has a relatively high ionization potential its compounds are predominantly covalent the ion does not exist. Boron does not react directly with hydrogen but the hydrolysis of magnesium boride does produce a range of boron hydrides. The species BH3 is only a short-lived reaction intermediate. 

Boron is a typical nonmetal, and most of its compounds are covalent. The most interesting compounds of boron are the covalent hydrides called boranes. We might expect BH3 to be the simplest hydride, since boron has three valence electrons to share with three hydrogen atoms. However, this compound is unstable, and the simplest known member of the series is diborane (B2H6), with the structure shown in Fig. 20.7(a). hi this... 

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