Boron boranes

Closely related to, but distinct from, the anionic boron and aluminum hydrides are the neutral boron (borane, BH3) and aluminum (alane, A1H3) hydrides. These molecules also contain hydrogen that can be transferred as hydride. Borane and alane differ from the anionic hydrides in being electrophilic species by virtue of the vacant p orbital and are Lewis acids. Reduction by these molecules occurs by an intramolecular hydride transfer in a Lewis acid-base complex of the reactant and reductant. 

In the absence of stabilization boron, borane tends to maintain die dimeric form. 

Kabalka, G. W., Guindi, L. H. M. Boron boranes in organic synthesis. Annual Survey covering the year 1989. J. Organomet. Chem. 1993, 457, 1-23. 

Niedenzu, K. Adv. Boron Boranes, Molecular Struct. Energetics 1988, 5, 357. 

The answer is to make use of yet another element boron. Boranes, including both BHj itself and analogues with one or two alkyl groups, HBR2 (an important example is shown in the margin), add to alkenes to make a new C—H bond and a new C—B bond by a mechanism we can write like this. The alkene pushes electrons into the boron s empty p orbital, while the hydrogen transfers onto the alkene. 

In this case the covalency of boron is brought up to four because the donor molecule supplies the necessary electrons. The adduct formed, trimethylamine-borane, is a stable white solid. Other compounds of a similar kind are known, all derived from the simple structure H3N -> BH3. This compound is isoelectronic with ethane, i.e. it contains the same number of electrons and has the same shape. 

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. 

We can consider the hydroboration step as though it involved borane (BH3) It sim phfies our mechanistic analysis and is at variance with reality only m matters of detail Borane is electrophilic it has a vacant 2p orbital and can accept a pair of electrons into that orbital The source of this electron pair is the rr bond of an alkene It is believed as shown m Figure 6 10 for the example of the hydroboration of 1 methylcyclopentene that the first step produces an unstable intermediate called a tt complex In this rr com plex boron and the two carbon atoms of the double bond are joined by a three center two electron bond by which we mean that three atoms share two electrons Three center two electron bonds are frequently encountered m boron chemistry The tt complex is formed by a transfer of electron density from the tt orbital of the alkene to the 2p orbital... 

Step 1 A molecule of borane (BH3) attacks the alkene Electrons flow from the 7C orbital of the alkene to the 2p orbital of boron A 7C complex is formed... 

Examine the electrostatic potential map of H3B THE (borane-tetrahydrofuran complex) on Learning By Modeling How does the electrostatic potential of the hydrogens bonded to boron dif fer from the potential of the hydrogens of the tetrahydrofuran ring" ... 

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. 

Hydrazine—borane compounds are made by the reaction of sodium borohydride and a hydrazine salt in THF (23,24). The mono-(N2H4 BH ) and di-(N2H4 2BH2) adducts are obtained, depending on the reaction conditions. These compounds have been suggested as rocket fuels (25) and for chemical deposition of nickel—boron alloys on nonmetallic surfaces (see Metallic COATINGS) (26). 

A number of less hindered monoalkylboranes is available by indirect methods, eg, by treatment of a thexylborane—amine complex with an olefin (69), the reduction of monohalogenoboranes or esters of boronic acids with metal hydrides (70—72), the redistribution of dialkylboranes with borane (64) or the displacement of an alkene from a dialkylborane by the addition of a tertiary amine (73). To avoid redistribution, monoalkylboranes are best used /V situ or freshly prepared. However, they can be stored as monoalkylborohydrides or complexes with tertiary amines. The free monoalkylboranes can be hberated from these derivatives when required (69,74—76). Methylborane, a remarkably unhindered monoalkylborane, exhibits extraordinary hydroboration characteristics. It hydroborates hindered and even unhindered olefins to give sequentially alkylmethyl- and dialkylmethylboranes (77—80). 

Monohalogenoboranes are conveniendy prepared from borane—dimethyl sulfide and boron trihahdes (BX where X = Cl, Br, I) by redistribution reaction, eg, for monochloroborane—dimethyl sulfide [63348-81-2] (9) (81—83). Other methods are also known (84—87). 

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