Inductive Effect on Acid and Base Strengths When an atom or group of atoms is substituted for another atom or group

of atoms in a molecule the distribution of electron density changes. The effect of the new atom or group of atoms on this electron density distribution is termed the "inductive effect" of the atom or group. If the new atom or group of atoms (the substituent) is more electronegative then the one that it replaced then electrons will be withdrawn from other parts of the molecule toward the new substituent. On the other hand if the new substituent is less electronegative than the group that it replaced then the electron density will increase in the rest of the molecule. Changes in substituents can have a profound effect on acidities and basicities of molecules and the relative strengths of structurally related acids and bases can be predicted on the basis of inductive effects of substituents. A more electronegative substituent X will increase the acidity of an oxy (or hydroxy) acid XO-H by greater withdrawal of electron density from the oxygen-hydrogen bond. This both weakens the O-H bond and increases the positive charge on hydrogen. A similar effect is present for the conjugate base XO1-; here the presence of a more electronegative substituent stabilizes the anion by withdrawing charge from the oxygen and effectively delocalizing the charge over more of the molecule. The pKa values for the X(O)n(OH)m acids on the following page illustrate this notion as do the pKa values of the larger series of the following simple acids: pKa Cl-OH 7.5 Br-OH 8.7 I-OH 10.7 HO-OH 11.8 H-OH 15.7 CH3OH 16.6 Note the effect of the CH3- group versus H-. The following series show a similar trend even though the substituent is not bonded directly to the ionizing hydroxyl group. pKa F-CH2C(O)OH 2.7 F-SO2-OH > Cl-SO2-OH > HO-SO2-OH Cl-CH2C(O)OH 2.8 Br-CH2C(O)OH 2.9 F2P(O)(OH) > FP(O)(OH)2 > HOP(O)(OH)2 I-CH2C(O)OH 3.0 H-CH2C(O)OH 4.7 CH3-CH2C(O)OH 4.9 Similar effects exist for bases. For example base strengths vary in the order NH3 > H2NNH2 > ClNH2 > Cl2NH > NF3, etc.

pKa values for acids of the type XOn(OH)m n=0 HOCl HOBr HOI HOClO HONO (HO)3PO (HO)3AsO HOClO2 HOIO3 HONO2 HOClO3 7.4 8.7 10.7 1.94 3.3 2.16 2.25 -1 0.7 -1.4 -10

n=1

7.21 7.77

12.3 11.6

n=2

n=3

pKa values for hydrated metal ions, [M(OH2)n]m+

Mm+ Th4+ Al3+ Y3+ La3+ Mg2+ Ca2+ Sr2+ Ba2+ pKa 3.2 5.0 7.7 8.5 11.4 12.8 13.3 13.5 Sc3+ Cr3+ Fe3+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Zn2+ Li+ Na+ K+ 13.6 14.2 14.5 Ag+ Tl+ 4.3 4.0 2.2 10.0 10.6 9.5 9.6 9.9 9.0 12.0 13.2 Mm+ pKa

pKa=-log K for [M(OH2)n]m+ + H2O = [M(OH2)n-1OH](m-1)+ + H3O+

How to recognize a Lewis Acid or Lewis Base For the average person there is probably most uncertainity about what molecules can act as Lewis acids. The following points should be helpful. 1) Molecules for which a simple Lewis structure indicates an atom does not have four pairs of electrons in its valence shell (an octet) will behave as Lewis acids. The electron deficient atom will have a vacant p orbital, although in reality there may be a pi interaction with one or more of the atoms bonded to it (BX3 for example). 2) Molecules whose Lewis structures indicate an atom to have an octet as a result of the formation of one or more multiple bonds will often function as Lewis acids. Examples are CO2, SO3, SO2. 3) Molecules that have central atoms that are capable of expanding their valence shell to include more than four pairs of sigma-bonding electron pairs, i.e., use hybrid orbitals that involve d orbitals, are Lewis acids. Examples are PCl5, SF4, I2 (recall the hybridization model for I3-), ICl3. Note, however, that alternative models can be used to describe the interaction of these acids with bases. A notable example is I2 in which the molecular orbital approach involves the interaction of the sigma antibonding orbital of the I2 with the donor orbital of the base. The acceptor orbital will normally be the LUMO. Lewis bases are typically easy to recognize. In principle any molecule in which there is an atom with a nonbonding, or lone, pair of electrons can function as a Lewis base. In practice there are certain types of molecules where the energies of the orbitals containing these nonbonding electrons are too low in energy to interact appreciably with most Lewis acids. Examples of such molecules are fluorine containing molecules. In some instances sigma bonding electrons are basic; group III (13) metal hydrides such as BH3, BH4- and AlH3 are examples. The resulting bonds are electron deficient, 3-center, 2-electron bonds. There are some molecules that have more than one basic site (there are termed ambidentate ligands when referring to coordination compounds). Examples are NCS-, NO2-, P[N(CH3)2]3. In molecular orbital terms, if the HOMO is nonbonding it will most often be the donor orbital but the nature of the acid can result in a lower energy orbital functioning as the donor orbital. Some molecules can function as either an acid or a base, for example SO2, and in a few instances as both acid and base. Examples of the latter are BH3, molecules in which there is intramolecular hydrogen bonding, and molecules such as (CH3)2B(CH2)3N(CH3)2 in which cyclization occurs by formation of a B-N bond.