Diborane compound

The sulfur-containing diborane compounds 39 were considered of potential interest as reagents in metal-catalyzed diboration reactions <2000AXC440>. 

Fig. 5. Molecular structures of some diborane compounds. Structure of B2(l,2-02-3-Me2C6H3)2 45, B-B bond length was determined as 1.315 A and structure of B2(l,2-02-3,5-tBu2C6H2)2(NHMe2)2, B-B bond length was found as 1.788 A Structure of B2(l,2-S2-4-MeC6H3)2 48, B-B length was determined as 1.737 A. Adapted by authors.

Subsequently, we calculated the B NMR chemical shifts both for the dimeric cyclic disubstituted boranes obtained via pathway A followed by dimerization and for the intramolecular B-H-B-bridging diborane compounds obtained via pathway B + E (Table 3). The calculated chemical shifts are listed alongside the experimental values in the range of +20 to +30 ppm (Table 3). The difficulties in assigning chemical shifts to specific species arose due to the 2 ppm error margin of both theoretical and experimental data. Despite this, many peaks were possible to assign accurately. In the case of D8, the expected... 

This is known as a hydrogen-bridge structure. There are not enough electrons to make all the dotted-line bonds electron-pairs and hence it is an example of an electron-deficient compound. The structure of diborane may be alternatively shown as drawn in... 

Aluminium tetrahydridoborate is a volatile liquid. It is the most volatile aluminium compound known. It is covalent and does not contain ions but has a hydrogen-bridge structure like that of diborane, i.e. each boron atom is attached to the aluminium by two hydrogen bridges ... 

Boranes are typical species with electron-deficient bonds, where a chemical bond has more centers than electrons. The smallest molecule showing this property is diborane. Each of the two B-H-B bonds (shown in Figure 2-60a) contains only two electrons, while the molecular orbital extends over three atoms. A correct representation has to represent the delocalization of the two electrons over three atom centers as shown in Figure 2-60b. Figure 2-60c shows another type of electron-deficient bond. In boron cage compounds, boron-boron bonds share their electron pair with the unoccupied atom orbital of a third boron atom [86]. These types of bonds cannot be accommodated in a single VB model of two-electron/ two-centered bonds. 

Figure 2-60. Soine examples of electron-deficient bonds a) diborane featuring B-H-B bonds b) diborane in a tentative RAMSES representation c) the orbital in a B-B-B bond (which occurs in boron cage compounds),...

Synthesis by high-dilution techniques requires slow admixture of reagents ( 8-24 hrs) or very large volumes of solvents 100 1/mmol). Fast reactions can also be carried out in suitable flow cells (J.L. Dye, 1973). High dilution conditions have been used in the dilactam formation from l,8-diamino-3,6-dioxaoctane and 3,6-dioxaoctanedioyl dichloride in benzene. The amide groups were reduced with lithium aluminum hydride, and a second cyclization with the same dichloride was then carried out. The new bicyclic compound was reduced with diborane. This ligand envelops metal ions completely and is therefore called a cryptand (B. Dietrich, 1969). 

Boron trifluoride is used for the preparation of boranes (see Boron compounds). Diborane is obtained from reaction with alkafl metal hydrides organoboranes are obtained with a suitable Grignard reagent. 

Diborane [19287-45-7] the first hydroborating agent studied, reacts sluggishly with olefins in the gas phase (14,15). In the presence of weak Lewis bases, eg, ethers and sulfides, it undergoes rapid reaction at room temperature or even below 0°C (16—18). The catalytic effect of these compounds on the hydroboration reaction is attributed to the formation of monomeric borane complexes from the borane dimer, eg, borane-tetrahydrofuran [14044-65-6] (1) or borane—dimethyl sulfide [13292-87-0] (2) (19—21). Stronger complexes formed by amines react with olefins at elevated temperatures (22—24). 

For adding dopiag impurities duriag vapor-phase growth, a gaseous or easily vaporizable Hquid compound is metered, added to the siUcon source gas stream, and reduced along with the siUcon compound. Typical examples are diborane, 2 phosphine, and boron tribromide, BBr. ... 

Thallium(1) salts of tetrahydridoborate and aluminate are obtained from a T1(I) compound, eg, ethoxide, perchlorate, or nitrate, and LiBH or LiAlH ia ether. ThaIlium(I) tetrahydridoborate [61204-71 -5] TIBH, is unstable at 40°C, evolving diborane. Thallium(I) tetrahydridoaluminate... 

Methylarsine, trifluoromethylarsine, and bis(trifluoromethyl)arsine [371-74-4] C2HAsF, are gases at room temperature all other primary and secondary arsines are liquids or solids. These compounds are extremely sensitive to oxygen, and ia some cases are spontaneously inflammable ia air (45). They readily undergo addition reactions with alkenes (51), alkynes (52), aldehydes (qv) (53), ketones (qv) (54), isocyanates (55), and a2o compounds (56). They also react with diborane (43) and a variety of other Lewis acids. Alkyl haUdes react with primary and secondary arsiaes to yield quaternary arsenic compounds (57). 

Dlbor ine(6). This compound is manufactured by Gallery Chemical Co. ia Gallery, Peimsylvania. Laboratory-scale preparations are given ia equations 4—64 5 6, of which the last may be the most convenient method. Diborane is the most important starting material for all the other boron hydrides. 

G in the presence of a catalytic amount of a Lewis base such as dimethylether, (GH2)20. In addition to the gas-phase pyrolysis of diborane, can be prepared by a solution-phase process developed at Union Garbide Gorp. Decaborane is a key intermediate in the preparation of many carboranes and metaHa derivatives. As of this writing, this important compound is not manufactured on a large scale in the western world and is in short supply. Prices for decaborane in 1991 were up to 10,000/kg. 

Despite the fact that many boron hydride compounds possess unique chemical and physical properties, very few of these compounds have yet undergone significant commercial exploitation. This is largely owing to the extremely high cost of most boron hydride materials, which has discouraged development of all but the most exotic appHcations. Nevertheless, considerable commercial potential is foreseen for boron hydride materials if and when economical and rehable sources become available. Only the simplest of boron hydride compounds, most notably sodium tetrahydroborate, NajBHJ, diborane(6), B2H, and some of the borane adducts, eg, amine boranes, are now produced in significant commercial quantities. 

Boron Hydrides" under "Boron Compounds" in ECT 1st ed., Vol. 2, pp. 593—600, by S. H. Bauer, Cornell University "Boron Hydrides and Related Compounds" under "Boron Compounds," Suppl. 1, pp. 103—130, by S. H. Bauer, Cornell University "Diborane and Higher Boron Hydrides" under "Boron Compounds," Suppl. 2, pp. 109—113, by W. J. Shepherd and E. B. Ayres, Gallery Chemical Company "Boron Hydrides" under "Boron Compounds" in ECT 2nd ed., Vol. 3, pp. 684—706, by G. W. Campbell, Jr., U.S. Borax Research Corporation "Boron Hydrides and their MetaHo Derivatives" under "Boron Compounds," in ECT 3rd ed., Vol. 4, pp. 135—183, by R. W. Rudolph, The University of Michigan. 

Boron Compounds (Boron Hydrides)" in ECT 1st ed., Vol. 2, pp. 593—600, "Boron Compounds (Boron Hydride and Related Compounds)" Suppl. 1, pp. 103—130, by S. H. Bauer, Cornell University "Boron Compounds (Diborane and Higher Boron Hydrides)" Suppl. 2, pp. 109—113, byj. W. Shepherd and... 

In this compound, synthesized in the low temperature reaction between diborane and excess ammonia, the cationic boron is coordinatively saturated in a tetrahedral environment. More recendy, cations having boron in tricoordinate or dicoordinate environments have been observed. These cationic species, called borenium and borinum ions, respectively, have been reviewed (19,20). 

Boron tribromide [10294-33A], BBr, is used in the manufacture of diborane and in the production of ultra high purity boron (see Boron, ELEMENTAL BoRON COMPOUNDS). Anhydrous aluminum bromide [7727-15-3], AIBr., is used as an acid catalyst in organic syntheses where it is more reactive and more soluble in organic solvents than AlCl. Tballium bromide [7789AOA], TlBr, is claimed as a component in radiographic image conversion panels (39). 

The most successful of the Lewis acid catalysts are oxazaborolidines prepared from chiral amino alcohols and boranes. These compounds lead to enantioselective reduction of acetophenone by an external reductant, usually diborane. The chiral environment established in the complex leads to facial selectivity. The most widely known example of these reagents is derived from the amino acid proline. Several other examples of this type of reagent have been developed, and these will be discussed more completely in Section 5.2 of part B. 

A solution of cholest-4-en-3-one (139), 1 g, in diethylene glycol dimethyl ether (20 ml) is treated for 1 hr with a large excess of diborane at room temperature under nitrogen and then left for a further 40 min. Acetic anhydride (10 ml) is added and the solution refluxed for 1 hr. The mixture is concentrated to a small volume, diluted with water and extracted with ether. The extracts are washed with 10% sodium hydroxide solution, then with water and dried over sodium sulfate. Removal of the solvent leaves a brown oil (1.06 g) which is purified by chromatography on alumina (activity I). Hexane elutes the title compound (141), 0.68 g mp 76-77°. Successive crystallization from acetone-methanol yields material mp 78-79°, [a]p 66°. 

The yellow compound BsF 2 appears to have a diborane-like structure (112) and this readily undergoes symmetrical cleavage with a variety of ligands such as CO, PF3, PCI3, PH3, ASH3 and SMe2 to give adducts L.B(BF2)3 which are stable at room temperature in the absence of air or moisture. 

X = alkyl, H, halogen, etc. They are usually colourless, crystalline compounds with mp in the range 0-100° for X = H and 50-200° for X = halogen. Synthetic routes, and factors affecting the stability of the adducts have already been discussed (p. 165 and p. 198). In cases where diborane undergoes unsymmetrical cleavage (e.g. with NH3) alternative routes must be devised ... 

F) 9 g of the diketo-pyrazino-morphanthridine compound obtained above are reduced with diborane to give mianserin. 

An important stage in the synthesis has been reached. The reaction processes described thus far have proceeded uneventfully and have culminated in the synthesis of compound 9. The stage is now set for an evaluation of the first of two hydroboration reactions. Treatment of 9 with diborane in THF, followed by standard alkaline hydrogen peroxide workup, furnishes an 8 1 stereoisomeric mixture of alcohols in favor of 28 (85 % total yield). On the basis of some important precedent,32 it is presumed that compound 9 preferen-... 

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