Photo- and Thermal Isomerization of (TP)Fe(CO)Cl<sub>2</sub> [TP = Bis(2-diphenylphosphinophenyl)phenylphosphine]
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Abstract
The
title complex displayed structural flexibility via photo- and
thermal-isomerization reactions between three isomers: (<i>mer</i>-TP)Fe(CO)Cl<sub>2</sub> (<b>A</b>), <i>unsym</i>-(<i>fac</i>-TP)Fe(CO)Cl<sub>2</sub> (<b>B</b>),
and <i>sym</i>-(<i>fac-</i>TP)Fe(CO)Cl<sub>2</sub> (<b>C</b>). Irradiation of <b>A</b> at RT with 525 nm
light selectively produces <b>B</b>, while at 0 °C isomer <b>C</b> is formed with the intermediacy of <b>B</b>. UV–vis
spectroscopy combined with TD-DFT calculations revealed the nature
of the photoisomerization process. Kinetics of the thermal isomerization
of <b>C</b> to <b>B</b> and <b>B</b> to <b>A</b> have been studied with <sup>31</sup>P NMR spectroscopy in CD<sub>2</sub>Cl<sub>2</sub>, and activation parameters were determined.
Isomers <b>A</b> and <b>B</b> have been isolated and crystallographically
characterized
