Chapter 6 Lecture 2 Hard-Soft Acid-Base Concepts Hard and Soft Acids and Bases Factors other than acid/base strength determine acid/base reactivity Silver Halide solubility AgX(s) + H2O Ag+(aq) + X-(aq) Ksp’s: AgF = 205, AgCl = 1.8 x 10-10, AgBr = 5.2 x 10-13, AgI = 8.3 x 10-17 Explanation of Solubility Solvation: F- much better solvated (small, high charge) Degree of Ag—X Interaction must also play a role HSAB Theory can help explain this data Hard acids/bases are small and nonpolarizable Soft acids/bases are large and polarizable Hard/Hard and Soft/Soft interactions are the most favorable Polarizable = easily distorted by other charged ions AgX data and HSAB Ag+ is large and polarizable = Soft Softness of Halides: I- > Br- > Cl- > F- AgI has the strongest interaction, thus the lowest solubility Softness is also associated with covalent bonds, not ionic bonds

5) Coordination of Thiocyanate (SCN-) to metal ions SCN- binds to large, polarizable metals, through S: Hg2+----SCN SCN- binds to smaller, less polarizable metals through N: Zn2+----NCS Explanation: Hard/Hard and Soft/Soft interactions are favored Exchange Reactions of [CH3Hg(H2O)]+ a) [CH3Hg(H2O)]+ + HCl CH3HgCl + H3O+ K = 1.8 x 1012 [CH3Hg(H2O)]+ + HF CH3HgF + H3O+ K = 4.5 x 10-2

7) LiX solubility: LiBr > LiCl > LiI > LiF Li+ is a hard ion LiF would be expected to be very ionic and soluble Very favorable hard-hard LiF interaction even overcomes solubility LiBr, LiCl are more soluble because of less favored interactions LiI is out of order because of poor I- solvation Pearson’s Hard and Soft Acids and Bases (1963) Most metal ions are hard acids (class a), some borderline depending on charge Large polarizable metal ions are soft (class b) Lewis bases can also be categorized as hard or soft Reactions favor hardness matches Hard/hard more energetically favored than soft/soft interactions Soft and borderline soft metal ions

6) Polarizability = degree to which an atom’s electron cloud is distorted by interactions with other ions Hard = small, compact charge, nonpolarizable = M3+, O2- Soft = large, polarizable = M0, S2- Comparison is easiest within a column of the periodic table

Pearson’s Absolute Hardness = h Quantitative method to measure hardness and softness, predict matches Formula uses Ionization energy (I) and Electron Affinity (A) Related to Mulliken’s definition of Electronegativity Defines Hardness as a large difference between I and A I = HOMO energy A = LUMO energy Softness = s = 1/h Halogens as an example a) Trend in h parallels HOMO energy (LUMO’s are about the same) b) F = most electronegative, smallest, least polarizable = hardest c) ClBrI h decreases as HOMO energy increases Problem: h doesn’t always match reactivity (hard, but still weak acid)

Drago’s Quantitative Approach -DH = EAEB + CACB DH = enthalpy of reaction for A + B AB E = capacity for ionic interactions (calculated from various reactions) C = capacity for covalent interactions (for various reactions) I2 used as reference E = 1.00, C = 1.00 Primarily covalent, so most E values > 1, most C values < 1

Frontier Orbitals and Acid-Base Chemistry Example: I2 + C6H6 I2 • C6H6 -DH = (1.00 x 0.681 + 1.00 x 0.525) = 1.206 kcal/mol (weak adduct) Advantages of Drago’s System Emphasis on the 2 factors involved in acid-base strength Electrostatics Covalency Pearson’s Hardness only considers covalency Good predictability if E and C have been tabulated If no data is available, Pearson’s HSAB method still allows for a rough prediction of the strength of an acid-base reaction Frontier Orbitals and Acid-Base Chemistry HOMO-LUMO Combination Acid-Base Reactions result in new product frontier orbitals Example: NH3 + H+ NH4+ NH3 lone pair reside in a1 MO = HOMO (base) H+ has only an empty 1s AO = LUMO (acid)

Combine these two orbitals to form a Bonding/ Antibonding pair Lone pair is stabilized in the new bonding orbital NH4+ is more stable than the separate NH3 and H+ Pick orbitals of similar symmetry and energy to combine If there is no match, there is no acid-base adduct formed

3) Symmetry, Energy, and Occupation of Frontier Orbitals allow us to predict the result of a given reaction a1 b1 b2

2 H2O + Ca Ca2+ + H2(g) + 2 OH- Ca HOMO >> H2O LUMO Not matched well for acid-base adduct to form Electron transfer (oxidation of Ca by H2O) is the predicted reaction n H2O + Cl- [Cl(H2O)n]- Correct energy match for acid-base adduct to form and be stable Water is the acid; its LUMO is used along with the base (Cl-) HOMO 6 H2O + Mg2+ [Mg(H2O)6]2+ Water is the base; its HOMO is used along with the LUMO of acid Mg2+ 2 H2O + 2 F2 4 F- + 4 H+ + O2 Water HOMO >> F2 LUMO Not matched well for an acid-base adduct to form Electron transfer (reduction of F2 by H2O) is the predicted reaction

4) Restating the Lewis Acid-Base Definition: a) Base: has e- pair in HOMO of correct energy and symmetry b) Acid: has LUMO of correct energy and symmetry HSAB using HOMO-LUMO a) Hard/Hard = simple electrostatics, little change in HOMO-LUMO energies, which remain far apart Soft/Soft = HOMO and LUMO close in energy combine to form energetically favorable new MO’s Hard/Hard is usually more favored than it appears due to +/-charge attraction

Carbon Monoxide as a Lewis Base 1) Electronegativity suggests O is the e- pair donor 2) In fact, C is always the donor a) Formal Charge b) MO Frontier Orbitals i. HOMO that is involved in bonding is mostly on C ii. C-like HOMO donated to the M Lewis acid

Hydrogen Bonding FHF- (symmetric, equivalent bonds to H) In chapter 5, we described the MO’s as H + F•F group orbitals Using a HOMO-LUMO Acid-Base description, we can use HF + F- F- HOMO (base) + HF LUMO and HOMO (acid) give 3 new MO’s Filled bonding MO of lowest energy Filled nonbonding (node through H) orbital Empty antibonding (nodes between all atoms) orbital of highest energy 3-center 2 electron bond, with ½ bond order per H—F bond

Unsymmetric BHA molecules are simplest example of Hydrogen Bonding Similar MO picture to that of FHF- Overall lower energy for the 2 e- pairs when bonded than unbonded 3 different possibilities for the energy match (a) Poor match: H2O + CH4 = overall higher energy; no H-bonding (b) Good match: H2O + HOAc = overall lower energy; strong H-bond (c) Very poor match: H2O + HCl = H atom transfer Why are electronegative atoms good at H-bonding? Low energy H—A HOMO similar in energy to H+ 1s orbital

D. Electronic Spectra of I2 (acid) + Donor (base) adducts

I2 gas: violet due to pg. su I2 gas: violet due to pg*su* transition (blue and red transmitted = purple) Nondonor hexane solvent causes no change = purple Donor solvents benzene and and methanol Donor HOMO interacts with su* LUMO of I2 New HOMO/LUMO energies of adduct shift spectrum Color (light transmitted) is changed Red-violet in benzene Yellow-brown in methanol KI/H2O solution with I2 forms I2—I- adduct I3- pg*su* energy increases, LUMO higher in energy toward blue ss* transition appears = Charge Transfer appears whenever a good donor interacts with I2 Charge transfer is so named because the transition occurs between an orbital mostly composed of one of the partners to an orbital mostly composed of the other partner

Charge Transfer in [Fe(H2O)5X]2+ complexes HOMO of X- increases in energy from F- to I- F- complex has closest HOMO-LUMO energy match forming a strong complex with stabilized new HOMO = colorless (all UV) Cl- complex has less interaction, new HOMO not stabilized as much, yellow color Br- even less interaction, less stabilization, yellow-brown color I- has no interaction, charge transfer only 2 Fe3+ + 2 I- 2 Fe2+ + I2 (purple color of I2 only)