PwrPts_CH_TI_Nernst_SS

PwrPts_CH_TI_Nernst_SS - 1.20 1.10 OMe OMe n OMe OMe OMe...

Info iconThis preview shows pages 1–6. Sign up to view the full content.

View Full Document Right Arrow Icon
• Curtin-Hammett principle • intramolecular electron transfer • cyclic voltammetry • Nernst equation • steady state kinetics • relative rates of cyclization • Thorpe-Ingold effect Topics
Background image of page 1

Info iconThis preview has intentionally blurred sections. Sign up to view the full version.

View Full DocumentRight Arrow Icon
HO S S H 3 CO OBn O OBn S S OCH 3 H 3 CO "anodic oxidation" Pt / C, MeOH 70% (!) HO S S H 3 CO OBn +1.16V +1.40 Duan & Moeller, JACS , 2002 , 124 , 9368 Despite the “doom” forecast by these values, the tetra- How can this be understood?
Background image of page 2
HO S S H 3 CO OBn - e HO S S H 3 CO BnO H intramolecular electron transfer HO MeO H 3 CO OBn H OMe 10% O OBn S S OCH 3 H 3 CO Curtin-Hammett principle exemplified HO S S H 3 CO OBn H
Background image of page 3

Info iconThis preview has intentionally blurred sections. Sign up to view the full version.

View Full DocumentRight Arrow Icon
What tool(s) is(are) available? Cyclic voltammetry … Oxidation begins i.e., -e Switching potential Peak potential Electron is beginning to be “returned” i.e., +e
Background image of page 4
p/2 +1.42 +1.40 +1.30
Background image of page 5

Info iconThis preview has intentionally blurred sections. Sign up to view the full version.

View Full DocumentRight Arrow Icon
Background image of page 6
This is the end of the preview. Sign up to access the rest of the document.

Unformatted text preview: +1.20 +1.10 OMe OMe n OMe OMe OMe OMe OMe OMe OMe OMe OMe OMe OMe OMe OMe OMe MeO OMe OMe OMe OMe OMe OMe OMe n OMe OMe n OMe OMe Pt anode, LiClO 4 10% MeOH/MeCN 2,6-lutidine, undivided cell Moeller & Tinao, J. Am. Chem. Soc. 1992 , 114 , 1033-1041 OMe OMe n OMe OMe n OMe OMe Pt anode, LiClO 4 10% MeOH/MeCN 2,6-lutidine, undivided cell SM k 1 k Š1 ( radical cation ) k 2 product k 8 ~ k 7 > k 6 > k 5 (gem methyls: Thorpe-Ingold effect) > k 5 “Communication” between the electrophores E obsd = E o Š RT/nF ln [ SM ] [ radical cation ] = E o Š RT/nF ln k Š1 + k 2 k 1 Note: Use of Nernst equation; application of steady state kinetics p/2 2...
View Full Document

This note was uploaded on 10/15/2010 for the course CHEM chem 127 taught by Professor Littlerd during the Fall '09 term at UCSB.

Page1 / 6

PwrPts_CH_TI_Nernst_SS - 1.20 1.10 OMe OMe n OMe OMe OMe...

This preview shows document pages 1 - 6. Sign up to view the full document.

View Full Document Right Arrow Icon
Ask a homework question - tutors are online