Octet exceptions

Stable if they have a filled valence shell of electrons. Atoms transfer or share electrons in such a way that they can attain a filled shell of electrons. This stable configuration of electrons is called an octet. Except for hydrogen and helium, a filled valence shell contains eight electrons. 

Provide a likely simple electronic structure for each of the following, assuming them to be completely covalent. Assume that every atom has a complete octet (except hydrogen, of course), and that two atoms may share more than one pair of electrons. 

All atoms have complete octets except nitrogen, which has a deficiency of two electrons. Use an electron pair from the terminal oxygen to form a double bond to nitrogen to complete its octet. The resulting structure is the best (most stable) for methyl nitrite. All atoms (except hydrogen) have eight electrons in their valence shell. 

Rule 3. (The octet rule) Depict all covalent bonds by two shared electrons, giving as many atoms as possible a surrounding electron octet, except for H, which requires a duet. Make sure that the number of electrons nsed is exactly the number counted according to rule 2. Elements at the right in the periodic table may contain pairs of valence electrons not used for bonding, called lone electron pairs or just lone pairs. 

IV. Each C, N, O and X atom must have an octet (exception carbocations [R3C ] are legal). 

More stable resonance form all atoms (except hydrogen) have octets of electrons... 

These examples illustrate the principle that atoms in covalently bonded species tend to have noble-gas electronic structures. This generalization is often referred to as the octet rule. Nonmetals, except for hydrogen, achieve a noble-gas structure by sharing in an octet of electrons (eight). Hydrogen atoms, in molecules or polyatomic ions, are surrounded by a duet of electrons (two). 

Determine the number of valence electrons required to fill out an octet for each atom (except H), in the skeleton. Remember that shared electrons are counted for both atoms. 

Reality Check Whenever you write a Lewis structure, check to see if it follows the octet rule. The structures written for OCl and C2H6 do just that each atom except H is surrounded by eight electrons. 

Exceptions to the Octet Rule Electron-Deficient Molecules... 

Octet rule The principle that bonded atoms (except H) tend to have a share in eight valence electrons, 166-171 exceptions to, 172-176 molecular geometry and, 181t molecular orbitals and, 650 Octyl acetate, 596t Open-pit copper mine, 540 Oppenheimer, J. Robert, 523 Optical isomer Isomer which rotates the... 

To check on the validity of a Lewis structure, verify that each atom has an octet or a duplet. As we shall see in Section 2.10, a common exception to this rule arises when the central atom is an atom of an element in Period 3 or higher. Such an atom can accommodate more than eight electrons in its valence shell. Consequently, the most stable Lewis structure may be one in which the central atom has more than eight electrons. 

The octet rule accounts for the valences of many of the elements and the structures of many compounds. Carbon, nitrogen, oxygen, and fluorine obey the octet rule rigorously, provided there are enough electrons to go around. However, some compounds have an odd number of electrons. In addition, an atom of phosphorus, sulfur, chlorine, or another nonmetal in Period 3 and subsequent periods can accommodate more than eight electrons in its valence shell. The following two sections show how to recognize exceptions to the octet rule. 

When different resonance structures are possible, some giving the central atom in a compound an octet and some an expanded valence shell, the dominant resonance structure is likely to be the one with the lowest formal charges. However, there are many exceptions and the selection of the best structure often depends on a careful analysis of experimental data. 

However, in this structure, boron does not have an octet. It has an empty p orbital, (very similar to a carbocation, except there is no positive charge here). Therefore, borane is very reactive. In fact, it reacts with itself to give dimeric structures, called diborane ... 

The structures used to show the bonding in covalent molecules are called Lewis structures. When bonding, atoms tend to achieve a noble gas configuration. By sharing electrons, individual atoms can complete the outer energy level. In a covalent bond, an octet of electrons is formed around each atom (except hydrogen.)... 

Atoms have different abilities to form bonds depending on their valence shell electrons. Most atoms present in polymers strive to meet an octet, i.e. eight electrons in their valence. (Hydrogen atoms are a very important exception, particularly in the case of polymers that contain more hydrogen atoms than carbon atoms.) To reach this goal, atoms form bonds. 

Lewis recognized that certain molecules such a PCI5 and SF6 are exceptions to the octet rule because their Lewis structures indicate that the central atom has more than eight electrons in its valence shell 10 for the P atom in PCI5 and the S atom in SF4, and 12 for the S atom in SFg (Figure 1.17). Such molecules are called hypervalent because the valence of the central atom is greater than its principal valence. To write a Lewis structure for such molecules, the Lewis symbol for the hypervalent atom must be modified to show the correct number of unpaired electrons. For the molecules in Figure 1.17 we would need to write the Lewis symbols as follows ... 

There are also molecules that are exceptions to the octet rule because one of the atoms has fewer, rather than more than, eight electrons in its valence shell in the Lewis structure (Figure 1.19). These molecules are formed by the elements on the left-hand side of the periodic table that have only one, two, or three electrons in their valence shells and cannot therefore attain an octet by using each of their electrons to form a covalent bond. The molecules LiF, BeCl2, BF3, and AIC13 would be examples. However, as we have seen and as we will discuss in detail in Chapters 8 and 9, these molecules are predominately ionic. In terms of a fully ionic model, each atom has a completed shell, and the anions obey the octet rule. Only if they are regarded as covalent can they be considered to be exceptions to the octet rule. Covalent descriptions of the bonding in BF3 and related molecules have therefore... 

Figure 1.19 Some examples of molecules that are exceptions to the octet rule because the central atom has fewer than eight electrons in its valence shell.

Not only molecules with LLPCN > 4, but all molecules of the elements in period 3 and beyond in their higher valence states, including most of their numerous oxides, oxoacids, and related molecules such as SO3 and (H0)2S04 should be regarded as hypervalent if AO bonds are described as double bonds (1). However, Lewis did not regard these molecules as exceptions to the octet rule because he wrote the Lewis structures of these molecules with single bonds and the appropriate formal charges (2). 

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