NOTES Structure Reactivity Relationships

Structure-Reactivity Relationships
A change in structure corresponds to a We want to view molecular

chemical reaction. Reactivity is the term we structure from the perspective of
use to describe the potential of a structure to potential to undergo chemical
undergo chemical change. Some structures change. A goal is to establish trends
are more prone to react than others. Structures that will allow you to examine a
that are likely to undergo chemical change are structure and make predictions
said to be reactive. Structures that are about its chemical characteristics.
resistant to chemical change are said to be Just like a physician diagnoses
unreactive. We sometimes choose to speak patients, chemists learn to associate
about the complementary property known as certain features of structure with the
stability. Structures that are highly reactive tendency to react. From these
are generally unstable. Structures that are trends emerge the structure-
unreactive are generally stable. reactivity relationships.
Potential energy (specifically, chemical potential) is the link between structure and reactivity.
The greater a structure’s chemical potential, the greater is its reactivity. Understanding the link
between structure and reactivity will help us decide which, among several possible changes, are
most reasonable (e.g., pathways having intermediates with exceedingly high energies are not
likely to be reasonable and should therefore be avoided, especially if a pathway with lower
energy intermediates is available).
structure chemical potential reactivity

Analysis of Chemical Potential
Analysis of Chemical Potential: Chemical potential makes sense in the context of a chemical reaction because we
can compare what’s on the two sides of a reaction arrow (→) and determine the difference in chemical potential.
By comparing what’s on one side with what’s on the other, it becomes possible to know if the chemical change is
favored or not. Does the left-hand-side or the right-hand-side have greater chemical potential? The favored
direction will be from high to low chemical potential.
An analysis of chemical potential can be done for individual elementary steps, or an overall chemical reaction, as
the problem demands. The things that contribute to chemical potential - the things that need to be compared - are:
• Bond energy changes
• Strength (reactivity) of electrophiles and /or acids
• Strength (reactivity) of nucleophiles and/or bases
A→B
Chemical potential for
the reaction A → B
GA
free energy
ΔG˚ = GB - GA
What Factors Contribute to High Chemical Potential?
• Weak bonds
GB • Low energy LUMO = strong acid (reactive electrophile)
• High energy HOMO = strong base (reactive nucleophile)
• Permanent charges
Factors Contributing to Charge Stability
Charged species are commonly encountered in chemical reactions, either as starting
components, end products, or as intermediates and TS≠ along a reaction pathway. There
is considerable energy associated with charged species; consequently, the relative
stability of charged atoms often provides important information about chemical
reactivity. The four factors listed below are some of the most important aspects of
structure that contribute to charge stability.
(1) Atom type and periodic table trends

________________________________ - The electronegativity and size
of charged atoms contribute to its ability to stabilize charge.
(2) Delocalization
____________________________ - All other things being equal, greater
charge delocalization leads to greater stability.
(3) Hybridization
________________________________ - All other things being equal, if
negative charge is localized on an atom, the greater the s-character of that
atom’s hybrid orbitals, the greater the stability (for negative charge: sp is
more stable than sp2, which in turn is more stable than sp3). Conversely, if
positive charge is localized on an atom, the lesser the s-character of that
atom’s hybrid orbitals, the greater the stability (for positive charge: sp3 is
more stable than sp2, which in turn is more stable than sp).
(4) Coulombic
_______________ Like charges repel; opposite charges attract.

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NOTES Structure Reactivity Relationships

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Structure-Reactivity Relationships

A change in structure corresponds to a We want to view molecular

structure chemical potential reactivity

(1) Atom type and periodic table trends

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