Issue 29, 2019

Photolysis of Tp′Rh(CNneopentyl)(PhNCNneopentyl) in the presence of ketones and esters: kinetic and thermodynamic selectivity for activation of different aliphatic C–H bonds

Abstract

The active fragment [Tp′Rh(CNneopentyl)], generated from the precursor Tp′Rh(CNneopentyl)(PhN[double bond, length as m-dash]CNneopentyl), underwent oxidative addition of substituted ketones and esters resulting in Tp′Rh(CNneopentyl)(R)(H) complexes (Tp′ = tris-(3,5-dimethylpyrazolyl)borate). These C–H activated complexes underwent reductive elimination at varying temperatures (24–70 °C) in C6D6 or C6D12. Using previously established kinetic techniques, the relative Rh–C bond strengths were calculated. Analysis of the relative Rh–C bond strengths vs. C–H bond strengths shows a linear correlation with slope RM–C/C–H = 1.22 (12). In general, α-substituents increase the relative Rh–C bond strengths compared to the C–H bond that is broken.

Graphical abstract: Photolysis of Tp′Rh(CNneopentyl)(PhNCNneopentyl) in the presence of ketones and esters: kinetic and thermodynamic selectivity for activation of different aliphatic C–H bonds

Supplementary files

Article information

Article type
Paper
Submitted
29 Mme 2019
Accepted
24 Mot 2019
First published
27 Mot 2019

Dalton Trans., 2019,48, 10945-10952

Author version available

Photolysis of Tp′Rh(CNneopentyl)(PhNCNneopentyl) in the presence of ketones and esters: kinetic and thermodynamic selectivity for activation of different aliphatic C–H bonds

A. M. Parsons and W. D. Jones, Dalton Trans., 2019, 48, 10945 DOI: 10.1039/C9DT01802F

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