Hard-Soft Acid-Base Theory

(HSAB)
• Helps explain preference for C- versus O-alkylation

1) Hard Acids: high + charge, small, low polarizability,

electrostatically dominated bonding and reactivity.

-Examples: Na+, H+, Mg2+, R3SiX

2) Hard Bases: High electronegativity, small, low

polarizability, electrostatically dominated bonding and
reactivity
-Examples: F-, OR-, PO43-, R2O

HSAB Theory (Continued)

3) Soft Acids: low + charge, large, high polarizability, covalent
chemistry (orbital controlled)

- Examples: Ag+, RHg+, Most C electrophiles (e.g., MeI).

4) Soft Bases: low electronegativity, large, polarizable, covalent

chemistry (orbital controlled)

- Examples: SR-, SR2, I-, carbon !-compounds

General Rule: Soft Acids and Soft Bases react and bond!
Hard Acids and Hard Bases react and bond!