Exploring generation of Rh(II) metalloradicals by photolysis of Rh(III)-X bond
Author ORCID
Abstract
Rhodium(II) metalloradicals featuring an unpaired electron on the d_(z^2 ) orbital display a pronounced role in small molecule activation due to its unique high reactivity. Although catalysis with Rh(II) porphyrins is enormously rare, one of the significant challenges lies in the tedious pathway to generate Rh(II) metalloradicals from Rh-CH3 specials, which are not directly available. Thus, this study outlines our efforts to develop the formation of Rh(II) metalloradical directly from the species having Rh(III)-X bond via photolysis. To achieve this goal, tetramesitylporphyrin (H2TMP) was synthesized and used as a precursor in the synthesis of tetramesitylporphyrinrhodium(III) iodide [(TMP)Rh(III)I]. Then this compound was employed for photolysis using different sources of light, i.e., UV lamp and Hg lamp. Furthermore, the preliminary reaction progress in photochemical experiments was analyzed by UV-vis spectroscopy and NMR.
Status
Graduate
Department
Chemistry & Biochemistry
College
College of Arts and Sciences
Campus
Athens
Faculty Mentor
Gao Wenyang
Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 4.0 International License.
Exploring generation of Rh(II) metalloradicals by photolysis of Rh(III)-X bond
Rhodium(II) metalloradicals featuring an unpaired electron on the d_(z^2 ) orbital display a pronounced role in small molecule activation due to its unique high reactivity. Although catalysis with Rh(II) porphyrins is enormously rare, one of the significant challenges lies in the tedious pathway to generate Rh(II) metalloradicals from Rh-CH3 specials, which are not directly available. Thus, this study outlines our efforts to develop the formation of Rh(II) metalloradical directly from the species having Rh(III)-X bond via photolysis. To achieve this goal, tetramesitylporphyrin (H2TMP) was synthesized and used as a precursor in the synthesis of tetramesitylporphyrinrhodium(III) iodide [(TMP)Rh(III)I]. Then this compound was employed for photolysis using different sources of light, i.e., UV lamp and Hg lamp. Furthermore, the preliminary reaction progress in photochemical experiments was analyzed by UV-vis spectroscopy and NMR.