ICH 231T

Questions for discussion: group 13 boron

Explain why boron never forms a 3-valent ion What is boron used for? Use your understanding of valence electrons to describe how boron reacts with oxygen, sulphur, nitrogen, chlorine and steam Use the reaction mechanism to predict the reaction of halides of boron with water Why does fluorine react differently? Why is borazine more accurately represented by a resonance structure? What is happening within this structure? Why do you propose it is possible for BN to form highly stable giant, or mega-molecules? ANSWERS:

General observations:
H

B + H N-

-N

H In borazine the difference in electronegativities of boron and nitrogen leads to electrophile attack at N and nucleophile attack at B

B+ H

B + H

N
H

Borazine is a colourless liquid with an aromatic odour and physical properties similar to benzene. If the compound has an odour there must be -bond activity. It has been found that the lone pair in nitrogen situated in one of the 2p orbitals interacts with the empty 2p orbital in boron this causes the -bond activity The B-N distances in the planar B3N3 ring are all equal (144pm) and close to the layered form of BN which is generally assumed to be triple bonded as a mega-molecule repeating as the N lone pair donates to successive B atoms (BN:BN:BN:BN:BN:BN:BN:BN:BN:) Because of the differences in electronegativity of N and B reactivity of borazine contrasts sharply with that of benzene

Other unusual applications: Metal borides are extremely hard, involatile, high melting & relatively inert structures. They are highly valuable industrially as refractory materials in rocket cones and turbine blades since they can withstand extreme stress, shock and high temperatures. Their formulae bear no resemblance to those expected on the basis of formal oxidation states of boron and the metal. They are prepared either by direct combination of the elements, or the metal oxides at high temperature. Metal borides may be either boride or metal rich and occur in the following general families: Boride rich: Metal rich: MB3, MB4, MB6, MB10, MB12, M2B5, M3B4 M3B, M4B, M5B, M3B2, and M7B3

Their structures are complex and diverse some examples Ni3B; Mn4B; Pd5B2; Cr5B2; Ta3B4; Li2B6 Distribution of B atoms is either as isolated; as pairs BB; as chains, linked double chains or sheets

Hydrides of boron simple hydrides borane BH3 has been isolated in the gas phase but is most stable & common as diborane B2H6 BH3 is electron deficient and can accept lone pairs as has been shown with H3N:BH3 This is due to -bond activity between the 2p orbitals. The same interaction occurs with other structures having a lone pair in a compatible orbital :CO the lone pair in the highest occupied molecular orbital of carbon is in a -bonding orbital which can connect to the vacant sp3 hybrid orbital of the tetrahedral BH3

What is unusual here is that the BH3 can also donate electrons from one of the B-H -orbitals to the lowest unoccupied orbital of CO which is a -orbital. The -bond donation from CO is the most significant and the exact extent of the hyper-conjugation is still not clearly understood. More complex halides cluster halides BnXn where X = Cl, Br or I Example B4Cl4 this structure has a tetrahedral core

At one time there was considerable interest in using boron hydrides as high energy fuels, but in practice it is difficult to ensure complete combustion to B2O3 and the involatile polymers which remain tend to block exhaust ducts Boron oxide, B2O3 the principal oxide of boron, is a 3-dimentional covalent structure comprising planar BO3 units which share oxygen atoms and are mutually twisted with respect to each other to form a ridged lattice.

USES of boron oxide

The glass industry of Western Europe and America accounts for about half the boron oxide produced. It is fused with SiO2 it forms borosilicate glass. This has the highest industrial use ovenware (pyrex glass) being an example. Fusion with appropriate metal oxides leads to coloured metal borate glass.