2P32 Principles of Inorganic Chemistry

Dr. M. Pilkington

Lecture 28 Elemental Boron Chemistry

1. Group 13 2. Boron compounds
Fundamental properties and the network Structural aspects of Boron chemistry

3. Borides 4. Halides 5. Group 13 - hydrides

Diborane and its chemistry

4. Boric acid and Borates 5. Organic compounds of Boron

1. Group 13
Because of their electron-deficient nature, Group 13 compounds containing the element (M) in the (+3) oxidation state have a formally vacant npz orbital and usually act as Lewis acids (electron acceptors). B Boron is a non metal. Al Aluminum takes its name from Alum, KAl(SO4)2.12H2O is used as an astringent, a substance that shrinks tissues and checks the flow of blood by contracting blood vessels. The ACS chemical society decided that the US would call the metal aluminum and the rest of the world calls the element aluminium. Ga- Gallium was discovered by a Russian Chemist in 1875. It was named after Gallus, the Latin name for territory that included what we know as modern France. Gallium is now obtained as a by product of the aluminum industry. As a solid at room temperature, it is a soft, bluish white metal that easily melts in the hand. It remains liquid upto 24030C, giving it the largest liquid range known.

In Indium was first identified in 1863 by Ferdinand Reich and his student who identified an indigo-colored emission line in zinc ore. (He identified the color but was color blind!). Tl Thallium was discovered in 1861 by Sir William Crookes, he analyzed selenium ores to find a beautiful green line previously unidentified. The element takes its name from thallos, the Greek word for green twig.

2. Boron Compounds
From the Aribic word Buraq and the Persian word Burah, which are both words for the material "borax. Uses: Boron was discovered by Joseph-Louis Gay-Lussac and Louis-Jaques Thnard, French chemists, and independently by Sir Humphry Davy, an English chemist, in 1808. They all isolated boron by combing boric acid (H3BO3) with potassium.

Today, boron is obtained by heating borax (Na2B4O710H2O) with carbon, although other methods are used if high-purity boron is required. Boron is used in pyrotechnics and flares to produce a green color. Boron has also been used in some rockets as an ignition source. Boron-10, one of the naturally occurring isotopes of boron, is a good absorber of neutrons and is used in the control rods of nuclear reactors, as a radiation shield and as a neutron detector. Boron filaments are used in the aerospace industry because of their highstrength and light weight. Boron forms several commercially important compounds. The most important boron compound is sodium borate pentahydrate (Na2B4O75H2O). Large amounts of this compound are used in the manufacture of fiberglass insulation and sodium perborate bleach. The second most important compound is boric acid (H3BO3), which is used to manufacture textile fiberglass and is used in cellulose insulation as a flame retardant.

important boron compound. Borax is used in laundry products and as a mild antiseptic. and as a potential medicine for treating arthritis.

Sodium borate decahydrate (Na2B4O710H2O), better known as borax, is the third most Other boron compounds are used to make borosilicate glasses, enamels for covering steel

Fundamental Group Properties of the Group 3A Elements

Fundamental Properties and the Network

Boron is involved in the uniqueness principle, the diagonal effect, and is a metalloid located on the metal-nonmetal line. Aluminium is diagonally related to Beryllium (both of which are metals on the metal-non metal line). Indium and thallium are involved in the inert pair effect. Inspection of the table reveals a few anomalies. Gallium has an atomic radius only 0.10 greater than that of aluminium and also higher than expected electronegativity (as do indium and thalium). The ionization energy of gallium is virtually the same as that for aluminium, rather lower than expected. Both anomalies can be traced back to the supposition that the nd10 and nf14 subshells are not particularly good at shielding succeeding electrons from the nuclear charge (see earlier lecture notes).

Structural Aspects of Boron Chemistry

The allotropic forms of boron are structurally complex and make it truly unique among all the elements. One of the principle recurring structural units in elemental boron is the B12 icosahedron (bottom left). These and related more complex units such as B84 (bottom right) do not pack at all well and result in many open spaces, leading to a low percentage of space occupied and a comparatively low density for the element. Remember allotropes are different molecular forms of the same element e.g. the allotropes of carbon are diamond, graphite, C60 and carbon nanotubes. The B84 unit found in some forms of boron is composed of a central B12 unit with an outwardly directed The B12 icosahedron it has 12 vertices, 20 triangular faces. pentagonal pyramid associated with each of the 12 atoms of the central unit

3. Borides
A wide range of binary metal borides. Formulas ranging from MB, MB2, M2B up to MB6, MB12 and even MB66. They are prepared by a wide variety of methods including most commonly (a) the direct combination of the elements; (b) the reduction of the corresponding metal oxide or chloride with boron, carbon, boron carbide or hydrogen and (c) the electrolysis of fused salts.

Representation of the variety of structures found in metal borides: (a) single atoms; (b) isolated pairs of atoms; (c) single strand chains; (d) branched singlestrand chains; (e) double chains of atoms; (f) two dimensional chicken wire infinite networks.

4. Halides
The halides of boron are BX3 are all volatile, highly reactive, covalently bonded, molecular compounds. BF3 and BCl3 are gases at RT. BBr3 is a liquid and BI3 is a white solid at RT. They are nonpolar trigonal planar molecules in which the boron atom is sp2 hybridized. To obtain electron density to fill the empty orbital, Group 13 compounds can also form partial multiple bonds with terminal atoms that contain lone pairs of electrons. The extent to which this happens depends on the energies of the AOs involved (the empty npz orbital and those of the lone pairs) and as you would expect from MO theory it happens mostly for Boron.

R X M R X M

R R

Where, for example,

= F

O R

R N R

Structure of the Halides

The B-X bond distances are shorter than might be expected, and the B-X bond energies are correspondingly higher. The B-F bond energy (646 KJmol-1) is the highest known for a single bond. All this has lead to the proposal that some -bonding may occur between the unhybridized 2p orbital of the boron and the filled np orbitals of the halides.

The structure of BX3 molecules. The boron atom is sp2 hybridized. Some evidence exists that some bonding may occur between the unhybridized 2p orbital of the boron and the filled (shaded) np orbitals.

The boron halides, like boric acid, are Lewis acids; that is they can readily accept a pair of electrons into their vacant, unhybridized p orbitals. For example

1. BF3 + F2. BF3 + R-O-R

BF4F3BOR2

In both cases, the negative reactant or the most partially negative part of the reactant attacks the central boron of the trifluoride.

5. Group 13 Hydrides
Special compounds that start of predominantly covalent and become more ionic as we go down the group. No BH3 as it does not exist as separate molecules The simplest hydride is B2H6 (2 different 1H NMR signals in a 4:2 ratio; 2 different IR stretching frequencies 2500 and 1600 cm-1) Why is this the case?

The Structure of B2H6 (diborane) multicentre bonds Contains a 3-centre-2-electron bond (called a banana bond)
H B H H H B H H

2-center-2 electron bond

3-center-2 electron bond

B sp3 hybridized

The structure of the three-centre, twoelectron bond in a B-H-B fragment of a diborane molecule. A pair of electrons in the bonding combination pulls all three atoms together. Bridging B-H have a bond order of and this accounts for the 1600 cm-1 B-H str in the IR. 4Hs terminal, 2Hs bridging accounts for the 1H-NMR spectrum. Other boron hydrides have similar bonding; B4H10, B5H9, B5H11, B10H14 etc

For the heavier elements, bridging is often observed if there are no other electron donors to provide electron density to the vacant orbital. If the substituents contain lone pairs of electrons, the bridges can be formed from two two-electron donoracceptor bonds:

R M R

X X M R R

When the substituents do not have any lone pairs of electrons, the bridges can be formed from from three-center-two-electron bonds (sometimes called banana bonds). Such bonds are readily explained by MO theory or a combination of VBT and MO theory:

H H

H B H B

H H
For the even more electropositive element Al, even methyl groups can bridge. e.g. [(C6F5)AlMe2]2

Diborane

Instead of using pure AOs the SALCs for this MO diagram are two sp3 hybrids from each B and the two 1s AOs for the bridging H atoms.

The Chemistry of B2H6

1. 2. 3. 4. 5. NaBH4 sodium borohydride an excellent reducing agent used in organic chemistry B2H6 spontaneously flammable in air B2H6 + O2 B2O3 + H2O VERY EXOTHERMIC B2H6 reacts with many Lewis bases, even weak ones: B2H6 + 2CO 2H3B-CO: also R3N: and R2O etc.. NaH + B2H6

Boric Acid B(OH)3

B2O3 + 3H2O

Boron oxide is an acid anhydride that reacts with water to afford boric acid. 2B(OH)3 Boric acid which in aq. solution is a mild antiseptic eye and mouthwash, has a planar structure.

The boron atom assumes sp2-hybridization whereas the oxygens are sp3. The VSEPR theory predicts that the O-B-O bond angle is 1200, whereas the B-O-H angle is somewhat less than 109.50, due to the presence of the two lone pairs on each oxygen.

The planar molecular structure of boric acid

In the solid, the single B(OH)3 units are hydrogen bonded into a planar, sheetlike structure which accounts for the flaky texture of the compound

The planar sheetlike structure of boric acid showing individual molecules (one highlighted) held together by hydrogen bonds (dashed lines).

Even though B(OH)3 is an acid, it is best to regard it using the Lewis definition. B(OH)3 acts as an acid by accepting a pair of electrons from an incoming OHion rather than transferring the proton to the hydroxide. Note the negative end of the hydroxide, oxygen atom, attacks the partially positive boron atom of the acid to produce a fourth B-OH bond. In the process the B assumes sp3 hybridization In the product, only one OH- ion is accepted Hence the compound is monobasic.

Borates
Variety of borate structures (a) orthoborate BO32-. (b) cyclic metaborate B3O62-; (c) chain metaborate BO2-; (d) perborate [B2(O2)2(OH)4]2-; (e) borax [B4O5(OH)4]2-. Metaborates occur when BO33- (borate) units link together to form chains or rings. Three dimensional borates range from simple to complex structures such as borax which contains the [B4O5(OH)4]2- anion.

5. Organic Compounds of Boron

The study of electron deficient boron compounds has contributed substantially to our understanding of the chemical bond. Research on boron compounds has ultimately led to two Nobel Prizes: H.C. Brown for the development of the hydroboration reaction (Nobel Prize in Chemistry 1979) William N. Lipscomb for his investigations of structure and bonding (Nobel Prize in Chemistry 1976 ) The great value of the hydroboration reaction lies in the large number of functional groups that can be introduced via boranes. H.C. shared his Nobel Prize with G. Wittig / who developed the chemistry of phosphorus ylides ("Wittig Reagents").

Boron as part of aromatic systems

The empty pz-orbital of boron can be part of delocalized, aromatic systems. Particularly interesting is the case of "borazine" a compound that is isoelectronic with benzene (the pair NB is equivalent to a CC double bond):

All substituents X with a lone pair stabilize the empty pz orbital on boron through intramolecular back-donation. The magnitude of back-donation decreases in the series R2N > RO > F. As a result, tris-alkoxyboranes (RO)3B and tris-aminoboranes (R2N)3B do not show any tendency to coordinate Lewis bases.

Polyboranes
Another consequence of the electron deficiency of the group 13 compounds is that they tend to form clusters under conditions where no other sources of electrons are available. The pyrolysis of B2H6 produces a variety of clusters and evolves H2 gas. Once formed, many of these polyboranes are stable compounds and many other elements can be placed into the skeleton of borane clusters including carbon, other main group elements and transition metals.

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