Molecular shapes with lone pair

Each set of hybrid orbitals is associated with a particular shape, although this may not coincide with the molecular shape if lone pairs also have to be accommodated ... 

Three common molecular shapes are associated with octahedral electron group geomehy. Most often, an inner atom with a steric number of 6 has octahedral molecular shape with no lone pairs. Example uses a compound of xenon, whose chemical behavior is described in the Chemical Milestones Box, to show a second common molecular shape, square planar. 

Step 4. Draw and name the molecular shape With four electron groups, one of them a lone pair, PF3 has a trigonal pyramidal shape (AX3E) ... 

Figure 11.5 shows the bonding in other molecular shapes with the tetrahedral electron-group arrangement. The trigonal pyramidal shape of NH3 arises when a lone pair fills one of the four sp orbitals of N, and the bent shape of H2O arises when lone pairs fill two of the sp orbitals of O. 

Step 4. Molecular shape With one lone pair, BrFj has the square pyramidal shape (AX5E) ... 

Follow the four-step process described in the flowchart. Begin with the Lewis structure. Use this stracture to determine the steric number, which indicates the electron group geometry. Then take into account any lone pairs to deduce the molecular shape. 

This relatively small catalog of molecular shapes accounts for a remarkable number of molecules. Even complicated molecules such as proteins and other polymers have shapes that can be traced back to these relatively simple templates. The overall shape of a large molecule is a composite of the shapes associated with its inner atoms. The shape around each inner atom is determined by steric numbers and the number of lone pairs. 

C09-0109. Species with chemical formula X I4 can have the following shapes. For each, name the molecular geometry, identify the ideal VSEPR bond angles, tell how many lone pairs are present in the structure, and give a specific example. 

The condensation reactions described above are unique in yet another sense. The conversion of an amine, a basic residue, to a neutral imide occurs with the simultaneous creation of a carboxylic acid nearby. In one synthetic event, an amine acts as the template and is converted into a structure that is the complement of an amine in size, shape and functionality. In this manner the triacid 15 shows high selectivity toward the parent triamine in binding experiments. Complementarity in binding is self-evident. Cyclodextrins for example, provide a hydrophobic inner surface complementary to structures such as benzenes, adamantanes and ferrocenes having appropriate shapes and sizes 12) (cf. 1). Complementary functionality has been harder to arrange in macrocycles the lone pairs of the oxygens of crown ethers and the 7t-surfaces of the cyclo-phanes are relatively inert13). Catalytically useful functionality such as carboxylic acids and their derivatives are available for the first time within these new molecular clefts. 

The reactivity of carbenes is strongly influenced by the electronic properties of their substituents. If an atom with a lone pair (e.g. O, N, or S) is directly bound to the carbene carbon atom, the electronic deficit at the carbene will be compensated to some extent by electron delocalization, resulting in stabilization of the reactive species. If both substituents are capable of donating electrons into the empty p orbital of the carbene, isolable carbenes, as e.g. diaminocarbenes (Section 2.1.6), can result. The second way in which carbenes can be stabilized consists in complexation. The shape of the molecular orbitals of carbenes enable them to act towards transition metals as a-donors and 71-acceptors. The chemical properties of the resulting complexes will also depend on the electronic properties of the metallic fragment to which the carbene is bound. Particularly relevant for the reactivity of carbene complexes are the ability of the metal to accept a-electrons from the carbene, and its capacity for back-donation into the empty p orbital of the carbene. 

In the approach of Puddephatt et al., the P-phenyl-phosphonitocavitand 2 was obtained by the reaction of phenylphosphonous chloride on re-sorc[4]arene lb (1, R=CH2CH2C6H5) in presence of pyridine as base. The reaction is stereoselective and yielded the bowl-shaped molecule 2 with the four P-phenyl groups directed outwards and the four lone pairs directed inwards ini configuration) [45-49] (Scheme 6). Molecular mechanics calculations performed on the six possible isomers of 2, showed that the iiii isomer is preferred and the orientation of one phenyl group toward the macrocyclic cavity is probable iiio isomer), but two or more phenyl groups oriented inwards are highly unlikely [48]. 

Likewise for the N()2 ion, the two 0 atoms must be treated the same way as participating in double-bond formation. All three atoms must use sp- orbitals, with end-overlap between each 0 and N to form cr bonds. And of course the three p orbitals that rise perpendicularly from their common plane will side-overlap and merge to give a delocalized split-banana-shaped n molecular orbital, with one half-banana above the plane of the molecule and the other half below (Figure 9-28). Four of the 18 valence electrons are held in the two cr bonds, 10 are held as five lone pairs in the sp- orbitals (two on each O, and one on the N), and the remaining four are delocalized over the length of the molecule in the n bond (two above the plane and two below). 

We also need to be able to deal with the effect of unpaired electrons. Radicals such as N02 have a single nonbonding electron. Such an electron is a region of high electron density and is treated like a lone pair when determining molecular shape. Thus, N02 (20) has a trigonal planar... 

The determinant (= total molecular wavefunction T) just described will lead to (remainder of Section 5.2) n occupied, and a number of unoccupied, component spatial molecular orbitals i//. These orbitals i// from the straightforward Slater determinant are called canonical (in mathematics the word means in simplest or standard form ) molecular orbitals. Since each occupied spatial ip can be thought of as a region of space which accommodates a pair of electrons, we might expect that when the shapes of these orbitals are displayed ( visualized Section 5.5.6) each one would look like a bond or a lone pair. However, this is often not the case for example, we do not find that one of the canonical MOs of water connects the O with one H, and another canonical MO connects the O with another H. Instead most of these MOs are spread over much of a molecule, i.e. delocalized (lone pairs, unlike conventional bonds, do tend to stand out). However, it is possible to combine the canonical MOs to get localized MOs which look like our conventional bonds and lone pairs. This is done by using the columns (or rows) of the Slater T to create a T with modified columns (or rows) if a column/row of a determinant is multiplied by k and added to another column/row, the determinant remains kD (Section 4.3.3). We see that if this is applied to the Slater determinant with k = 1, we will get a new determinant corresponding to exactly the same total wavefunction, i.e. to the same molecule, but built up from different component occupied MOs i//. The new T and the new i// s are no less or more correct than the previous ones, but by appropriate manipulation of the columns/rows the i// s can be made to correspond to our ideas of bonds and lone pairs. These localized MOs are sometimes useful. 

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