Photochemical electron transfer initiated oxidative fragmentation of aminopinacols. Factors governing reaction rates and quantum efficiencies of C-C bond cleavage

H. Gan, U. Leinhos, Ian Gould, D. G. Whitten

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

The fragmentation reactions of the cation radicals of a series of remote diamine-substituted pinacols have been investigated. The cation radicals were generated upon photooxidation with excited 2,6,9,10-tetracyanoanthracene in acetonitrile. The products are consistent with cleavage of the central C-C bond. The rate constants for fragmentation were determined both from steady-state quantum yield studies and from time-resolved measurements. In general, the rate constants for fragmentation increase with increasing stability of the radical and cation products. However, the results of temperature dependence studies clearly demonstrate that conformational effects play an important role in the transition state. In some cases, these conformational effects can result in changes in the reactivity order expected from purely thermodynamic considerations.

Original languageEnglish (US)
Pages (from-to)3566-3573
Number of pages8
JournalJournal of Physical Chemistry
Volume99
Issue number11
StatePublished - Jan 1 1995
Externally publishedYes

Fingerprint

Quantum efficiency
Reaction rates
Cations
quantum efficiency
cleavage
electron transfer
fragmentation
reaction kinetics
Positive ions
cations
Electrons
Rate constants
Diamines
Photooxidation
photooxidation
Quantum yield
products
diamines
Time measurement
Acetonitrile

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

Photochemical electron transfer initiated oxidative fragmentation of aminopinacols. Factors governing reaction rates and quantum efficiencies of C-C bond cleavage. / Gan, H.; Leinhos, U.; Gould, Ian; Whitten, D. G.

In: Journal of Physical Chemistry, Vol. 99, No. 11, 01.01.1995, p. 3566-3573.

Research output: Contribution to journalArticle

@article{d44302ecbe4f43788b95874d66c515ba,
title = "Photochemical electron transfer initiated oxidative fragmentation of aminopinacols. Factors governing reaction rates and quantum efficiencies of C-C bond cleavage",
abstract = "The fragmentation reactions of the cation radicals of a series of remote diamine-substituted pinacols have been investigated. The cation radicals were generated upon photooxidation with excited 2,6,9,10-tetracyanoanthracene in acetonitrile. The products are consistent with cleavage of the central C-C bond. The rate constants for fragmentation were determined both from steady-state quantum yield studies and from time-resolved measurements. In general, the rate constants for fragmentation increase with increasing stability of the radical and cation products. However, the results of temperature dependence studies clearly demonstrate that conformational effects play an important role in the transition state. In some cases, these conformational effects can result in changes in the reactivity order expected from purely thermodynamic considerations.",
author = "H. Gan and U. Leinhos and Ian Gould and Whitten, {D. G.}",
year = "1995",
month = "1",
day = "1",
language = "English (US)",
volume = "99",
pages = "3566--3573",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - Photochemical electron transfer initiated oxidative fragmentation of aminopinacols. Factors governing reaction rates and quantum efficiencies of C-C bond cleavage

AU - Gan, H.

AU - Leinhos, U.

AU - Gould, Ian

AU - Whitten, D. G.

PY - 1995/1/1

Y1 - 1995/1/1

N2 - The fragmentation reactions of the cation radicals of a series of remote diamine-substituted pinacols have been investigated. The cation radicals were generated upon photooxidation with excited 2,6,9,10-tetracyanoanthracene in acetonitrile. The products are consistent with cleavage of the central C-C bond. The rate constants for fragmentation were determined both from steady-state quantum yield studies and from time-resolved measurements. In general, the rate constants for fragmentation increase with increasing stability of the radical and cation products. However, the results of temperature dependence studies clearly demonstrate that conformational effects play an important role in the transition state. In some cases, these conformational effects can result in changes in the reactivity order expected from purely thermodynamic considerations.

AB - The fragmentation reactions of the cation radicals of a series of remote diamine-substituted pinacols have been investigated. The cation radicals were generated upon photooxidation with excited 2,6,9,10-tetracyanoanthracene in acetonitrile. The products are consistent with cleavage of the central C-C bond. The rate constants for fragmentation were determined both from steady-state quantum yield studies and from time-resolved measurements. In general, the rate constants for fragmentation increase with increasing stability of the radical and cation products. However, the results of temperature dependence studies clearly demonstrate that conformational effects play an important role in the transition state. In some cases, these conformational effects can result in changes in the reactivity order expected from purely thermodynamic considerations.

UR - http://www.scopus.com/inward/record.url?scp=0029272230&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0029272230&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0029272230

VL - 99

SP - 3566

EP - 3573

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 11

ER -