Group borides

The methods for preparing polycrystalline borides often require high T. The only exceptions are precipitations of a few Fe and Pt group borides from aq soln however high-T treatments are necessary to form crystalline compounds. 

Borides have metallic characteristics such as high electrical conductivity and positive coefficients of electrical resistivity. Many of them, particularly the borides of metals of Groups 4 (IVB), 5 (VB), and 6 (VIB), the MB compounds of Groups 2(11) and 13(111), and the borides of aluminum and siUcon, have high melting points, great hardness, low coefficients of thermal expansion, and good chemical stabiUty. 

The various stoichiometries are not equally common, as can be seen from Fig. 6.5 the most frequently occurring are M2B, MB, MB2, MB4 and MBfi, and these five classes account for 75% of the compounds. At the other extreme RunBg is the only known example of this stoichiometry. Metal-rich borides tend to be formed by the transition elements whereas the boron-rich borides are characteristic of the more electropositive elements in Groups 1-3, the lanthanides and the actinides. Only the diborides MB2 are common to both classes. 

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. 

Silicides of groups I and 2 are generally much more reactive than those of the transition elements (cf. borides and carbides). Hydrogen and/or silanes are typical products e.g. ... 

The most extensive group of nitrides are the metallic nitrides of general formulae MN, M2N, and M4N in which N atoms occupy some or all of the interstices in cubic or hep metal lattices (examples are in Table 11.1, p. 413). These compounds are usually opaque, very hard, chemically inert, refractory materials with metallic lustre and conductivity and sometimes having variable composition. Similarities with borides (p. 145) and carbides (p. 297) are notable. Typical mps (°C) are ... 

The binary borides (p. 145), carbides (p. 299), and nitrides (p. 418) have already been discussed. Suffice it to note here that the chromium atom is too small to allow the ready insertion of carbon into its lattice, and its carbide is consequently more reactive than those of its predecessors. As for the hydrides, only CrH is known which is consistent with the general trend in this part of the periodic table that hydrides become less stable across the d block and down each group. 

Methyl a-D-mannopyranoside was treated in succession with p-toluene-sulfonyl chloride, carbonyl chloride, and benzoyl chloride, and, without isolating the intermediates, there was obtained in 37% yield methyl 4-0-l enzoyl-2,3-O-carbony 1-6-0-(p-tolylsulfonyl ) -D-mannoside. The tos-yloxyl group of the latter was replaced by iodine, and hydrogenation of the 6-iodo derivative in the presence of a nickel boride catalyst gave methyl 4-0-benzoyl-2,3-0-carbonyl-6-deoxy- -D-mannoside. Treatment of the latter with hydrogen bromide in acetic acid gave crystalline 4-0-benzoyl-2,3-0-carbonyl-6-deoxy-a-D-mannosyl bromide (8) (16). The... 

Although boron forms borides with many elements, only the borides of the transition metals have been investigated extensively for their CVD characteristics. Boron forms stable borides with the transition metals, and the most refractory of these and those with the greatest potential interest are the borides of the elements of Groups IVa (Ti, Zr, Hf), Va (V, Nb, Ta) and, to a lesser degree. Via (Cr, Mo, W) (see Table... 

Borides of Group IVa. UB2, ZrB2, and HfB2 are readily deposited by the hydrogen reduction of the metal halide, usually the chloride. Atypical reaction is as follows ... 

The Group IVa borides can also be deposited with diborane as a boron source in a pressure range ofafewTorrto 1 atm as follows ... 

Borides of Group Va. The borides of Group Va, Nb2, and TaB2, are more difficult to deposit than those of Group IVa, since the incorporation of free metal in the deposit is difficult to avoid. However, relatively pure deposits can be obtained by the co-reduction of the bromides at high temperatures (1500°C) and low pressure, or by the coreduction of the chlorides if the molar gas mixture is preheated to 700-800°C just before entering the reactor.t ] The incorporation of free... 

Borides of Group Via. As with the borides of Group Va, the incorporation of free metal in the Group Via borides is difficult to avoid. Both tungsten and molybdenum borides are obtained at high temperature by the hydrogen reduction of the mixed bromides.Bonding appears a more effective method to form these borides in thin layers (see Sec. 2.2 above). 

Carbides oxidize readily although less rapidly than the nitrides but more so than the borides. Oxidation becomes more rapid going from the Group IV carbides (TiC, ZrC, HfC) to those of Group VI (Cr3C7, MoC, WC). In some cases, a protective film of the metal oxide is formed. Such is the case with SiC, as reviewed in Sec. 5.7 below. 

Thiophenes can also be desulfurized to alkenes (RCH2CH=CHCH2R from 115) with a nickel boride catalyst prepared from nickel(II) chloride and NaBILj in methanol.It is possible to reduce just one SR group of a dithioacetal by treatment... 

It is helpful to divide the boride structures into four partially overlapping groups based primarily on the arrangement of B atoms ... 

Figure 1 presents a scheme for the formation of B—B bonds in binary metal borides, i.e., the occurrence of one-, two- and three-dimensional B aggregates as a function of the periodic group of the metal constituent. 

Considering the mode of filling the voids in the metal framework of rj phases with the Ti2Ni type (see Ref. 1) (Table 1), Re3Al2B is the only boride member of this group, with B atoms entering the large icosahedral center in 16d, occupied by metal... 

The cubic UB, 2-type boride structure with space group Fm3m can be described on the basis of a B,2-cubooctahedron (see Fig. 1) . The association of the B,2-poly-hedra by oriented B—B bonds gives rise to a three-dimensional skeleton with boron cages. Formally, the arrangement of the B,2-units and of the metals atoms is of the NaCl-type. Each metal is located in the center of a B24-cubooctahedron. 

---