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Volumn 48, Issue 4, 2009, Pages 1356-1369

Autoxidation of platinum(IV) hydrocarbyl hydride complexes to form platinum(IV) hydrocarbyl hydroperoxide complexes

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EID: 64349113645     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic801216r     Document Type: Article
Times cited : (50)

References (101)
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    • 2 and consistent AIBN concentrations) both argue against an impurity origin of the autoacceleration.
    • 2 and consistent AIBN concentrations) both argue against an impurity origin of the autoacceleration.
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    • Reactions with low AIBN concentrations (0.03-0.1 mM) were more rapid than expected. See the Supporting Informationfor more details.
    • Reactions with low AIBN concentrations (0.03-0.1 mM) were more rapid than expected. See the Supporting Informationfor more details.
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    • Since only a small amount of 3a is generated during the reaction, it is not clear whether there is an inverse dependence on this compound. However, experiments in which 3a was added to the solution proceeded at a slightly slower rate (Figure 9), indicating that the inverse dependence is likely relative to the total platinum concentration, 1a + 2a + 3a, rather than just 1a + 2a.
    • Since only a small amount of 3a is generated during the reaction, it is not clear whether there is an inverse dependence on this compound. However, experiments in which 3a was added to the solution proceeded at a slightly slower rate (Figure 9), indicating that the inverse dependence is likely relative to the total platinum concentration, 1a + 2a + 3a, rather than just 1a + 2a.
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    • At long reaction times, the data deviate from linearity because, as the concentration of 1a approaches 0, the baseline noise in the NMR spectra becomes significant relative to the signal intensity. Only the linear portion (through 94-98% conversion) of the data was used for the regression analysis and figures
    • At long reaction times, the data deviate from linearity because, as the concentration of 1a approaches 0, the baseline noise in the NMR spectra becomes significant relative to the signal intensity. Only the linear portion (through 94-98% conversion) of the data was used for the regression analysis and figures.
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    • 1 likely depends upon the initiator concentration, but the nature of the dependence could not be determined. The autocatalytic process dominates the reaction, and large uncertainties hampered interpretation of the k1 calculated values. See the Supporting Information.
    • 1 likely depends upon the initiator concentration, but the nature of the dependence could not be determined. The autocatalytic process dominates the reaction, and large uncertainties hampered interpretation of the k1 calculated values. See the Supporting Information.
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    • Similar to the autoxidation of 1a (see ref 46, the data deviate from linearity as the concentration of 1b approaches 0. The problem is more pronounced for 1b than 1a since the baseline-resolved NMR signals which could be integrated corresponded to fewer protons. Only the linear portions of the data (through 50-75% conversion) were used for the regression analysis and figures
    • Similar to the autoxidation of 1a (see ref 46), the data deviate from linearity as the concentration of 1b approaches 0. The problem is more pronounced for 1b than 1a since the baseline-resolved NMR signals which could be integrated corresponded to fewer protons. Only the linear portions of the data (through 50-75% conversion) were used for the regression analysis and figures.
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