Jump to main content
Jump to site search

Issue 29, 2019
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Supplementary files

Article information


Submitted
29 Apr 2019
Accepted
24 May 2019
First published
27 May 2019

Dalton Trans., 2019,48, 10945-10952
Article type
Paper
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

Social activity

Search articles by author

Spotlight

Advertisements