Diborane acidity

Diborane or aUcylboranes are used for reduaion of alkenes and alkynes via hydrobora-tion (see pp. 37f., 47f., 130f.) followed by hydrolysis of the borane with acetic acid (H.C. Brown, 1975). 

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). 

Sodium borobydride reacts with Lewis acids in nonprotic solvents to yield diborane [19287-45-7] 2 6 which can then be used to generate other useful organoboranes such as amine boranes, alkyl boranes, and boron hydride clusters. 

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. 

Chemical Reactivity - Reactivity with Water Reacts to form flammable hydrogen gas Reactivity with Common Materials Reacts with acids to form toxic, flammable diborane gas. Slowly attacks and destroys glass Stability During Transport Stable unless contaminated with acids or is overheated, thereby forming flammable hydrogen gas Neutralizing Agents for Acids and Caustics Caustic formed by the reaction with water can be diluted with water and then neutralized with acetic acid Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

Diakyl carbamyl chlorides Diakyl aluminum hydrides Diborane Dibromoketone Dichloromethyl chloroformate Diphosgene Fuming nitric acid Gngnard reagents Hydrides nonvolatile... 

Bell and Hall have incorporated an organometallic unit into a crown by using the ferrocenyl unit as part of the ring or as a third strand. The unit is incorporated either as the 1,1 -diformylferrocene or the corresponding acid. In the former case, the bis-imine is prepared and reduced to give the saturated crown (see structure 24). In the latter case, the acid is converted into its corresponding chloride and thence into the diamide by reaction with a diamine. Diborane reduction affords the saturated amino-crown. Structure 24 could be prepared by either of these methods but the dialdehyde approach was reported to be poor compared to the amide approach which afforded the product in ca. 60% yield . 

Contrary to Brown s results, a later paper claims that chloral, esters and acid chlorides are readily reduced by diborane in tetrahydrofuran it is suggested that diborane can complex with tetrahydrofuran before effecting reduction. 

Diborane occupies a special place because all the other boranes can be prepared from it (directly or indirectly) it is also one of the most studied and synthetically useful reagents in the whole of chemistry.B2H6 gas can most conveniently be prepared in small quantities by the reaction of I2 on NaBH4 in diglyme [(MeOCH2CH2)20], or by the reaction of a solid tetrahydroborate with an anhydrous acid ... 

Free borane (2) exists as gaseous dimer—the diborane BaHg. In addition Lewis acid/Lewis base-complexes, as for example formed in an ethereal solvent, e.g. 4, are commercially available ... 

Condensation of adipic acid derivative 17 with phenylethylamine in the presence of carbo-nyldiimidazole affords the bis-adipic acid amide 18. The synthesis is completed by reduction of the carbonyl groups with diborane followed by demethylation of the aromatic methoxy groups with hydrogen bromide the afford dopexamine (19) [3]. 

Diborane reacts with ammonia to form an ionic compound (there are no other products). The cation and anion each contain one boron atom, (a) Predict the identity and formula of each ion. (b) Give the hybridization of each boron atom, (c) Identify the type of reaction that has occurred (redox, Lewis acid-base, or Bronsted acid-base). 

Nitric acid forms explosive mixtures with boranes, especially diborane. 

The situation does not improve with mixtures with the hydrides of the elements. Thus, a detonation occurred during contact between water and chlorine due to an accidental spark. Phosphine, silane and diborane all combust spontaneously in chlorine (their behaviour is the same in oxygen). With hydrogenated nitrogenous compounds ammonia, hydrazine, hydroxylamine, ammonium salts (especially ammonium chloride), and also sulphamic acid (these last two in an acid medium) there is ignition or even detonation. 

Boron trichloride Boron trifluoride Fluoroboric acid Potassium tebafluoroborate Boric acid Boron nitride Sodium perborate Diborane... 

Diborane also has a useful pattern of selectivity. It reduces carboxylic acids to primary alcohols under mild conditions that leave esters unchanged.77 Nitro and cyano groups are relatively unreactive toward diborane. The rapid reaction between carboxylic acids and diborane is the result of formation of a triacyloxyborane intermediate by protonolysis of the B-H bonds. The resulting compound is essentially a mixed anhydride of the carboxylic acid and boric acid in which the carbonyl groups have enhanced reactivity toward borane or acetoxyborane. 

The diborane is generated (in situ, or separately, from NaBH4 and Et2Offi—BF3e), and probably complexes, as the monomeric BH3, with the ethereal solvent used for the reaction. BH3 is a Lewis acid and adds to the least substituted carbon atom of the alkene (Markownikov addition), overall addition is completed by hydride transfer to the adjacent, positively polarised carbon atom ... 

Interaction of sodium and other tetrahydroborates with anhydrous acids (fluorophos-phoric, phosphoric or sulfuric) to generate diborane is very exothermic, and may be dangerously violent with rapid mixing. Safer methods of making diborane are detailed. 

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