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• Structures with a positive formal charge on carbon • What hybridization will carbocations have?
• What geometry will carbocations have?
– trigonal planar
R C R R
• Carbocations are inherently unstable due to
– Incomplete octet for carbon – Positive charge
• However, some are not as bad as others • Substituents that release electrons will stabilize carbocations by spreading the charge over a larger volume • Substituents that withdraw electrons will destabilize carbocations by packing a greater charge onto the carbon
2° primary C+.Electron Release/Withdrawal Mechanisms • Induction – Induction involves the push and pull of electrons through sigma bonds – Example: bromine is more electronegative than carbon and will pull at the electrons in their sigma bond • Resonance => STRONGER EFFECT – Resonance involves the push and pull of electrons through a pi system Electron Releasing Substituents • Inductive only – Alkyl groups H3C CH3 C CH3 is more stable than H C is more stable than H C H H3C CH3 H3C tertiary C+. much more stable than having the entire charge on one atom Problem 1 • Draw resonance structures to demonstrate which atoms in the structure below share H H the positive charge C H H H H H 2 . 1° • Resonance – Atoms with lone pairs – Alkenyl groups – Aromatic rings OH H3C C CH3 H3C OH C CH3 Structure has 1/2 of positive charge on each atom. 3° secondary C+.
because NO reaction occurs Curved arrows are used to show movement of electrons (NOT atoms) Resonance Hybrid Problem 2 • Rank the following carbocations from most to least stable H C H H H CH3 C H H H C C H CH3 C H CH3 H C H Two electron-releasing substituents.Notes on resonance forms: None of the Lewis structures to the right are exact representations of the electron and charge positions in the molecule (none actually exist and the molecule does NOT resonate between them) H H C H H H H C H H H H H H H H Four Resonance Forms H H H H H C H H The behavior of the molecule is best described as a HYBRID of the resonance forms.25 H +0. but provide charge stabilization by the weaker inductive mechanism through sigma-bond framework H C H C H H C H H CH3 C CH3 H CH3 C H H H C H Least stable. no electron-releasing substituents Most stable as single electron-releasing substituent provides resonance stabilization by sharing the positive charge between two atoms 3 .25 H H H H H H H H +0.25 H Notes on arrows: The double-headed arrows are used between resonance forms instead of reaction arrows.25C H +0. H H C H +0.
Electron Withdrawing Substituents • Electronegative atoms (at least those more electronegative than O): Br. and partial charges. 1° Problem 3 • Which of the groups below is the MOST electron-withdrawing? • Hint: draw out each complete Lewis structure with electrons. O NO2 Br C H O OCH3 C O N O Full formal positive charge on nitrogen makes this group very electron-withdrawing 4 . Cl. I. formal charges. 1° H H3C C H + H is more stable than HC O C H primary C . F • Groups with positive (or partial positive charges) H H3C C H is more stable than H Br C H primary C+.