Electron placement

We can t draw a single electron-dot structure that indicates the equivalence of the two 0-0 bonds in 03 because the conventions we use for indicating electron placement aren t good enough. Instead, the idea of resonance is indicated by drawing the two (or more) individual electron-dot structures and using a double-headed resonance arrow to show that both contribute to the resonance... 

Figure 4 BeCb structures (a) monomer, (b) dimer, and (c) polymer. Solid lines represent covalent bonds and arrowed lines represent coordinate (Lewis base — Lewis acid) bonds. Note that the depicted structure is in resonance with other formal electron placement schemes. Thus, on average, all Be-Cl interactions appear equivalent...

Curved arrows Arrows that show the direction of electron flow in chemical reactions also used to show differences in electron placement between resonance forms. 

Many molecules can be represented by two or more Lewis structures that differ only m the placement of electrons In such cases the electrons... 

The two Kekule structures for benzene have the same arrangement of atoms but differ m the placement of electrons Thus they are resonance forms and neither one by Itself correctly describes the bonding m the actual molecule As a hybrid of the two Kekule structures benzene is often represented by a hexagon containing an inscribed circle... 

The valence theory (4) includes both types of three-center bonds shown as well as normal two-center, B—B and B—H, bonds. For example, one resonance stmcture of pentaborane(9) is given in projection in Figure 6. An octet of electrons about each boron atom is attained only if three-center bonds are used in addition to two-center bonds. In many cases involving boron hydrides the valence stmcture can be deduced. First, the total number of orbitals and valence electrons available for bonding are determined. Next, the B—H and B—H—B bonds are accounted for. Finally, the remaining orbitals and valence electrons are used in framework bonding. Alternative placements of hydrogen atoms require different valence stmctures. 

The two individual line-bond structures for acetate are called resonance forms, and their special resonance relationship is indicated by the doubleheaded arrow between them. The only difference between resonance forms is the placement of the r and nonbonding valence electrons. The atoms themselves occupy exactly the same place in both resonance forms, the connections between atoms are the same, and the three-dimensional shapes of the resonance forms are the same. 

Resonance forms differ only in the placement of their tt or nonbonding electrons. Neither the position nor the hybridization of any atom changes from one resonance form to another. In the acetate ion, for example, the carbon atom is sp2-hybridized and the oxygen atoms remain in exactly the same place in both resonance forms. Only the positions of the r electrons in the C=0 bond and the lone-pair electrons on oxygen differ from one form to another. This movement of electrons from one resonance structure to another can be indicated by using curved arrows. A curved arrow always indicates the movement of electrons, not the movement of atoms. An arrow shows that a pair of electrons moves from the atom or bond at the tail of the arrow to the atom or bond at the head of the arrow. 

With all these advantages one might well wonder why the left-step table has not attracted more attention and indeed why it has not been widely adopted. The answer to this question lies in the placement of one crucial element, helium. In the left-step table, helium is placed among the alkaline earth metals as mentioned above. To most chemists this is completely abhorrent since helium is regarded as the noble gas par excellence. Meanwhile, to a physicist or somebody who emphasizes electronic properties, helium falls rather naturally into the alkaline earths since it has two outer-shell electrons. 

Notice that, unlike the sulfite ion, which has three resonance forms, the presence of the hydrogen ion restricts the electrons to the oxygen atom to which it is attached. Because H is electropositive, its placement near an oxygen atom makes it less likely for that oxygen atom to donate a lone pair to an adjacent atom. 

Similar electron accessibility generates similar chemical behavior. For example, iodine has many more electrons than chlorine, but these two elements display similar chemical behavior, as reflected by their placement in the same group of the periodic table. This is because the chemistry of chlorine and iodine is determined by the number of electrons in their largest and least stable occupied orbitals 3 S and 3 p for chlorine and 5 S and 5 p for iodine. Each of these elements has seven accessible electrons, and this accounts for the chemical similarities. 

A clue to the nature of the third itt MO can be found in the placement of electrons in the two resonance structures for ozone, which are shown with color highlights in Figure 10-36a. Notice that in one resonance structure, the left outer atom has three lone pairs and a single bond, while the right outer atom has two lone pairs and a double bond. In the other resonance structure, the third lone pair is on the right outer atom, with the double bond to the left outer atom. The double bond appears in different positions in the two stmctures, and one of the lone pairs also appears in different positions. These variations signal delocalized orbitals. 

Nevertheless, the placement of two Cl atoms on the C and C carbon atoms of the NHC skeleton, the presence of the strong SO Ar electron-withdrawing group on the aryl A-substituents, or the modification of the NHC skeleton from an imidazol-to a triazol-type, have allowed to fill the gap between the TEP of phosphines and NHCs, see Pig. 1.14. 

---