Boron covalent bonding

In Group III, boron, having no available d orbitals, is unable to fill its outer quantum level above eight and hence has a maximum covalency of 4. Other Group 111 elements, however, are able to form more than four covalent bonds, the number depending partly on the nature of the attached atoms or groups. 

The covalently bonded oxygen atom still has two lone pairs of electrons and can act as an electron pair donor. It rarely donates both pairs (to achieve 4-coordination) and usually only one donor bond is formed. A water molecule, for example, can donate to a proton, forming H30, and diethyl ether can donate to an acceptor such as boron trifluoride ... 

Boron is similar to carbon in that it has a capacity to form stable covalently bonded molecular networks. Carbonates, metalloboranes, phosphacarboranes, and other families comprise thousands of compounds. 

The electron counts of nitrogen in ammonium ion and boron in borohydride ion are both 4 (half of eight electrons in covalent bonds) Because a neutral nitrogen has five electrons in its valence shell an electron count of 4 gives it a formal charge of +1 A neutral boron has three valence electrons so that an electron count of 4 in borohydride ion corresponds to a formal charge of -1... 

When a sibcon crystal is doped with atoms of elements having a valence of less than four, eg, boron or gallium (valence = 3), only three of the four covalent bonds of the adjacent sibcon atoms are occupied. The vacancy at an unoccupied covalent bond constitutes a hole. Dopants that contribute holes, which in turn act like positive charge carriers, are acceptor dopants and the resulting crystal is -type (positive) sibcon (Fig. Id). 

Amine—borane adducts have the general formula R3N BX where R = H, alkyl, etc, and X = alkyl, H, halogen, etc. These compounds, characterized by a coordinate covalent bond between boron and nitrogen, form a class of reducing agents having a broad spectmm of reduction potentials (5). 

The reaction between a trinuclear metal carbonyl cluster and trimetbyl amine borane has been investigated (41) and here the cluster anion functions as a Lewis base toward the boron atom, forming a B—O covalent bond (see Carbonyls). Molecular orbital calculations, supported by stmctural characterization, show that coordination of the amine borane causes small changes in the trinuclear framework. 

Boron is a covalently bonded, refractory, non-metallic insulator of great hardness and is thus not directly comparable in its physical properties with Al, Ga, In and Tl, which are all low-melting, rather soft metals having a very low electrical... 

Notice that the beryllium atom has no unpaired electrons, the boron atom has one, and the carbon atom two. Simple valence bond theory would predict that Be, like He, should not form covalent bonds. A boron atom should form one bond, carbon two. Experience tells us that these predictions are wrong. Beryllium forms two bonds in BeF2 boron forms three bonds in BF3. Carbon ordinarily forms four bonds, not two. 

The electron configuration (41) is somewhat higher in energy than (40). It is necessary to promote a 2s electron to the 2p state to obtain (41). In return, however, the boron atom gains bonding capacity. Whereas a boron atom can form only one covalent bond in configuration... 

The boron atom in BF5 can complete its octet if an additional atom or ion with a lone pair of electrons forms a bond by providing both electrons. A bond in which both electrons come from one of the atoms is called a coordinate covalent bond. For example, the tetrafluoroborate anion, BF4 (31), forms when boron trifluoride is passed over a meral fluoride. In this anion, the formation of a coordinate covalent bond with a fluoride ion gives the B atom an octet. Another example of a coordinate covalent bond is that formed when boron trifluoride reacts with ammonia ... 

The Lewis structure of the product, a white molecular solid, is shown in (32). In this reaction, the lone pair on the nitrogen atom of ammonia, H3N , can be regarded as completing boron s octet in BF3 by forming a coordinate covalent bond. 

Boron trichloride, a colorless, reactive gas of BC13 molecules, behaves chemically like BF3. However, the trichloride of aluminum, which is in the same group as boron, forms dimers, linked pairs of molecules. Aluminum chloride is a volatile white solid that vaporizes at 180°C to a gas of Al2Cl6 molecules. These molecules survive in the gas up to about 200°C and only then fall apart into A1C13 molecules. The Al,CI6 molecule exists because a Cl atom in one AlCI, molecule uses one of its lone pairs to form a coordinate covalent bond to the Al atom in a neighboring AICI molecule (33). This arrangement can occur in aluminum chloride hut not boron trichloride because the atomic radius of Al is bigger than that of B. 

Boron forms perhaps the most extraordinary structures of all the elements. It has a high ionization energy and is a metalloid that forms covalent bonds, like its diagonal neighbor silicon. However, because it has only three electrons in its valence shell and has a small atomic radius, it tends to form compounds that have incomplete octets (Section 2.11) or are electron deficient (Section 3.8). These unusual bonding characteristics lead to the remarkable properties that have made boron an essential element of modern technology and, in particular, nan otechn ol ogy. 

In the crystal structure of these phases with tetragonal symmetry (P4/mbm, D h) the boron covalent sublattice is formed by chains of octahedra, developing along the c axis and by pairs of B atoms, bonding the octahedra in the xOy plane (see Fig. 1). The resulting three-dimensional skeleton contains tunnels parallel to the c axis that are filled by metal atoms . ... 

Trimethylboron is an example of one type of Lewis acid. This molecule has trigonal planar geometry in which the boron atom is s hybridized with a vacant 2 p orbital perpendicular to the plane of the molecule (Figure 21-11. Recall from Chapter 9 that atoms tend to use all their valence s and p orbitals to form covalent bonds. Second-row elements such as boron and nitrogen are most stable when surrounded by eight valence electrons divided among covalent bonds and lone pairs. The boron atom in B (CH ) can use its vacant 2 p orbital to form a fourth covalent bond to a new partner, provided that the new partner supplies both electrons. Trimethyl boron is a Lewis acid because it forms an additional bond by accepting a pair of electrons from some other chemical species. 

The simplest type of Lewis acid-base reaction is the combination of a Lewis acid and a Lewis base to form a compound called an adduct. The reaction of ammonia and trimethyl boron is an example. A new bond forms between boron and nitrogen, with both electrons supplied by the lone pair of ammonia (see Figure 21-21. Forming an adduct with ammonia allows boron to use all of its valence orbitals to form covalent bonds. As this occurs, the geometry about the boron atom changes from trigonal planar to tetrahedral, and the hybrid description of the boron valence orbitals changes from s p lo s p ... 

Ammonia reacts with boron trichloride to form a molecule called an adduct or Lewis acid base complex in which the lone pair on the ammonia molecule is shared with the boron atom to form a covalent bond and completing an octet on boron (Figure 1.16) ... 

It has been found by Will (2004) from X-ray scattering measurements that valence electrons concentrate along the lines connecting the boron atoms, confirming that the boron layer is a covalently bonded network. The titanium layers are metallic. However, the layers are not characteristic of either pure Ti, or pure B, so the bonding is quite complex. 

It is known that boronic acids can bind with hydroxyl compounds, including polyols such as PVA, through the complex formation of a reversible covalent bonding [56, 57]. 

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