Boron borazine

The emphasis in the approaches to boron nitride [10043-11 -5] BN, precursors has been concentrated on cycHc compounds. There have been recent reports of trimethylsilyl-substituted aminoboranes being evaluated as B—N precursors. These are linear borylamines containing up to four boron atoms. Compounds were also synthesized with free —NH2 groups amenable to condensation with either dihaloboranes or dihaloborazines (65) and offering suitable monomers for linear B—N polymer synthesis and borazine-ring-linking appHcations. 

Borazine, B3N3Hft, a compound that has been called inorganic benzene because of its similar hexagonal structure (but with alternating B and N atoms in place of C atoms), is the basis of a large class of boron—nitrogen compounds. Write its Lewis structure and predict the composition of the hybrid orbitals used by each B and N atom. 

One of the first reports related to the preparation of macrocyclic ring systems with boron atoms deals with the transformation of m-difunctionalized borazines into cyclic di-, tetra-, or hexaborazines [16-19]. 

Borazine Pyrolysis Studies. In a simplistic manner, one can visualize the formation of boron nitride via stepwise eliminations between rings, i.e.,... 

The most studied class of boron polymers containing boron-silicon bonds are the carboranylenesiloxane polymers. The history of these polymers was discussed at the beginning of this chapter. The more recent advances in this group of polymers and in silicon-containing borazine and boroxine polymers are discussed in later sections of this chapter. In this section, some remaining groups of silicon-containing boron polymers are discussed. 

The best known boron-containing ring systems are the so-called inorganic benzenes, namely, borazine (71), boroxine (72), and triphosphatriborin (73) (Fig. 46), which are isoelectronic and isostructural with benzene. These ring systems are obtained by the interaction of boron with nitrogen, oxygen, and phosphorus, respectively.4... 

Figure 46 The planar structures of the boron ring systems, borazine (71) and boroxine (72), with nonexistent aromaticities and of triphosphatriborin (73) with an appreciable degree of aromaticity. (Adapted from ref. 95.)...

The area of organoboron polymers containing borazine and its derivatives is covered in Chapter 5 of this book by Miele and co-workers. Miele and Bernard also describe the utilization of these polymers in ceramics, fibers, and so on, in Chapter 3 of this book. In this section, the utilization of polymers containing borazine or in some cases the bicyclic boron ligand, 9-BBN, for the production of SiC or Si/C/B fibers is briefly described. Recent advances in polypyrazolylborate or pyrazabole-containing polymers and other boron ring system-derived polymers also have been briefly described. 

The introduction of small amounts of boron into precursors that produce silicon nitride have been known to improve the ceramic yields of silicon nitride and Si—B—C—N ceramics as first reported in 1986.110 Several reports have appeared in the past couple of years alone that utilize borazine precursors such as 2,4-diethylb-orazine and other cyclic boron precursors, such as pinacolborane, 1,3-dimethyl-1, 3-diaza-2-boracyclopentane, for their reactions with silanes, polysilazanes, and polysilylcarbodiimides for the high-yield production of Si—B—N—C ceramics.111... 

The nB NMR spectrum of the product showed two broad signals at 27.7 ppm and 24.7 ppm, which are attributed to boron atoms of the borazine ring and the boryl substituents, respectively. These results are consistent with the formation of the /i-tri [bis( methy lam ino (boryl (methyl jam ino]borazine 13 as the main product (Fig. 6). No free B(NHCH3)3 was detected. 

Generally, during hydroboration polymerization of dicyano compounds, the formation of the borazine structures that have a six-membered boron-nitrogen ring (scheme 19a) and dihydroborated end groups (scheme 19b) as a structural defect is unavoidable. The borazine cross-linked structures often cause the gelation, and dehydroboration causes a decrease in molecular weight. 

There is a great deal of potential interest in borazine as a precursor of boron nitride, since it offers the advantages of being a single source of boron and nitrogen with the correct B/N ratio and a high ceramic yield. In addition, borazine contains the elementary BN building block as its substituted derivatives. This is described later. 

In this section, syntheses of a variety of inorganic nitrogen compounds are described. The syntheses include those of triazanium chlorides alkylamino derivatives of boron, arsenic, and tin and trimeric and tetrameric boron-nitrogen ring structures as exemplified by borazine (HNBH)3. 

The original method1 reported for the preparation of trichloroborazine involves the use of borazine. However, this procedure is not recommended because of the difficulty of preparing this heterocycle and its hydrolytic instability. More recently, this trichloroborazine has been prepared directly from ammonium chloride and boron trichloride at elevated temperatures with or without a solvent.2-8 Ammonium chloride may be replaced by a primary aliphatic or aromatic amine or its hydrochloride, and organodihaloboranes can be used in place of the boron trichloride to give the respective N- and B-substituted borazines.6 Boron tribromide has been used in analogous reactions to yield -B,/ , .B"-tribromoborazines.6... 

Compounds belonging to the borazine structural class which is based on a six-membered ring of alternating boron and nitrogen atoms are readily prepared by a number of reactions including... 

The trichloro derivative having a chlorine atom bound to each of the boron atoms is known as B-trichloroborazine. Borazine can be prepared by several different methods, one of which is the reduction of the trichloro compound ... 

Boron also forms many other compounds with nitrogen. One of the most interesting of these is bora-zine, B3N3HS (m.p. -58 °C, b.p. 54.5 °C). Shown here is the structure ofborazine, which is similar to the structure of benzene. In fact, borazine has sometimes been referred to as "inorganic benzene."... 

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