Record Details

Title:
Initial metal–metal bond breakage detected by fs X-ray scattering in the photolysis of $Ru_{3}(CO)_{12}$ in cyclohexane at 400 nm
Affiliation(s):
EuXFEL staff, Other
Author group:
Instrument FXE
Topic:
Abstract:
Using femtosecond resolution X-ray solution scattering at a free electron laser we were able to directly observe metal–metal bond cleavage upon photolysis at 400 nm of $Ru_{3}(CO)_{12}$, a prototype for the photochemistry of transition metal carbonyls. This leads to the known single intermediate $Ru_{3}(CO)_{11}(μ-CO)*$, with a bridging ligand (μCO) and where the asterisk indicates an open Ru3-ring. This loses a CO ligand on a picosecond time scale yielding a newly observed triple bridge intermediate, $Ru_{3}(CO)_{8}(μ-CO)_{3}*$. This loses another CO ligand to form the previously observed $Ru_{3}(CO)_{10}$, which returns to $Ru_{3}(CO)_{12}$ via the known single-bridge $Ru_{3}(CO)_{10}(μ-CO)$. These results indicate that contrary to long standing hypotheses, metal–metal bond breakage is the only chemical reaction immediately following the photolysis of $Ru_{3}(CO)_{12}$ at 400 nm. Combined with previous picosecond resolution X-ray scattering data and time resolved infrared spectroscopy these results yield a new mechanism for the photolysis of $Ru_{3}(CO)_{12}$.
Imprint:
Royal Society of Chemistry, 2019
Journal Information:
Photochemical & Photobiological Sciences, 18 (2), 319-327 (2019)
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Language(s):
English
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