Beryllium covalent bonding

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. 

Beryllium, at the head of Group 2, resembles its diagonal neighbor aluminum in its chemical properties. It is the least metallic element of the group, and many of its compounds have properties commonly attributed to covalent bonding. Beryllium is amphoteric and reacts with both acids and alkalis. Like aluminum, beryllium reacts with water in the presence of sodium hydroxide the products are the beryl-late ion, Be(OH)42, and hydrogen ... 

The standard reduction potential for Be2+ is the least negative of the elements in the group and by the same token beryllium is the least electropositive and has the greatest tendency to form covalent bonds. The bulk metal is relatively inert at room temperature and is not attacked by air or water at high temperatures. Beryllium powder is somewhat more reactive. The metal is passivated by cold concentrated nitric acid but dissolves in both dilute acid and alkaline solutions with the evolution of dihydrogen. The metal reacts with halogens at 600°C to form the corresponding dihalides. 

As it does not have any unshared electrons, beryllium would not be expected to form a covalent bond. But experimentally it is found that beryllium is able to form two covalent bonds. To form these bonds one electron moves from the 2s orbital to the 2p orbital leaving the atom in an excited state with two unpaired electrons (Figure 4b). 

Beryllium is normally divalent in its compounds and, because of its high ionic potential, has a tendency to form covalent bonds. In free BeX2 molecules, the Be atom is promoted to a state in which the valence electrons occupy two equivalent sp hybrid orbitals and so a linear X—Be—X system is found. However, such a system is coordinatively unsaturated and there is a strong tendency for the Be to attain its maximum coordination of four. This may be done through polymerization, as in solid BeCk, via bridging chloride ligands, or by the Be acting as an acceptor for suitable donor molecules. The concept of coordinative saturation can be applied to the other M"+ cations, and attempts to achieve it have led to attempts to deliberately synthesize new compounds. 

The Third-Group Elements.—The B—F bond has about 63 percent ionic character, B—O 44 percent, B—Cl 22 percent, and so forth. Bor,on forms normal covalent bonds with hydrogen. The aluminum bonds are similar to those of beryllium in ionic character. 

All group 2 elements are metals, but an abrupt change in properties between Be and Mg occurs as Be shows anomalous behavior in forming mainly covalent compounds. Beryllium most frequently displays a coordination number of four, usually tetrahedral, in which the radius of Be2+ is 27 pm. The chemical behavior of magnesium is intermediate between that of Be and the heavier elements, and it also has some tendency for covalent bond formation. 

Now according to covalent bond theory, each beryllium-hydrogen bond must consist of two electrons, shared between the two different atoms. One of these electrons is contributed by the hydrogen, while the other comes from the beryllium atom. 

Some of the halides of the alkaline earth metals have a similar identity problem. Calcium chloride and magnesium chloride have melting points almost as high as that of sodium chloride. Those compounds are clearly held together by ionic bonds. Beryllium chloride, on the other hand, melts at about half the temperature of table salt. And it boils at 520°C compared to salt s 1,465°C. The differences in properties are due to the partially covalent bond formed between beryllium and chlorine. 

Some pertinent data for the elements are given in Table 4-1. Beryllium has unique chemical behavior with a predominantly covalent chemistry, although it forms an aqua ion [Be(H20)4]2+. Magnesium has a chemistry intermediate between that of Be and the heavier elements, but it does not stand in as close relationship with the predominantly ionic heavier members as might have been expected from the similarity of Na, K, Rb, and Cs. It has considerable tendency to covalent bond formation, consistent with the high charge/radius ratio. For instance, like beryllium, its hydroxide can be precipitated from aqueous solutions, whereas hydroxides of the other elements are all moderately soluble, and it readily forms bonds to carbon. 

The paper discusses two types of reaction involving metal complexes, and it is postulated that each proceeds by an initial free-radical step. In reactions between metal carbonyls and N2O4—NO2 mixtures, the nature of the product depends upon the phase in which the reaction is carried out. In the liquid phase, where the predominant equilibrium is N204 N0+ + NO3-, metal nitrates or carbonyl nitrates are formed in the gas phase, where the equilibrium is N2O4 2NO2/ nitrites or their derivatives are produced. Reactions of Mn2(CO) o Fe(CO)5, Co2(CO)3, and Ni(CO)4 are discussed. Anhydrous metal nitrates in which the nitrate group is covalently bonded to the metal have enhanced reactivity. This is believed to result from the dissociation M—O—N02 M—O + NO2 This can explain the solution properties of beryllium nitrates, and the vigorous (even explosive) reaction of anhydrous copper nitrate with diethyl ether. 

A. Most covalent compounds of beryllium. Be. Because Be contains only two valence shell electrons, it usually forms only two covalent bonds when it bonds to two other atoms. We therefore vise four electrons as the number needed by Be in step 2, Section 7-5. In steps 3 and 4 we use only two pairs of electrons for Be. 

Alkalis and alkaline earths almost exclusively form ionic chemical bonds with nonmetallic elements. Consequently, these elements tend to exist almost entirely as salts or oxides. Only beryllium shows a tendency toward covalent bonding. 

The octet rule predicts that atoms form enough covalent bonds to surround themselves with eight elechons each. When one atom in a covalently bonded pair donates two electrons to the bond, the Lewis structure can include the formal charge on each atom as a means of keeping track of the valence electrons. There are exceptions to the octet rule, particularly for covalent beryllium compounds, elements in Group 3A, and elements in the third period and beyond in the periodic table. 

Beryllium hydride is formed in a similar fashion. Here the overlap is between the sp hybrid orbitals of the beryllium atom and the partly filled Is orbital from each of two hydrogen atoms, to give two covalent bonds. 

The implication of the above structural data is that the second-row metals—lithium and beryllium—are using all of their low-energy orbitals (2s and 2p) and that evidence for directional, covalent bonding of these metals might be found as opposed to a nondirectional, predominantly ionic bonding for the heavier Group la and Ha metals. 

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