A photochemical procedure for determining reaction quantum efficiencies in systems with multicomponent inner filter...

Area of Science:

• Photochemistry
• Chemical Kinetics
• Organometallic Chemistry

Background:

• Measuring photochemical quantum efficiencies is crucial for understanding reaction mechanisms.
• Overlapping absorbances and inner filter effects complicate photochemical analyses.
• Metal complex photochemistry, including ligand substitution and C-H/Si-H bond activation, often exhibits these challenges.

Purpose of the Study:

• To describe a kinetic procedure for accurately measuring photochemical quantum efficiencies in complex reaction mixtures.
• To validate the method for systems with significant inner filter effects.
• To demonstrate the application in quantifying Si-H bond activation photochemistry of a specific rhodium complex.

Main Methods:

• Development of a kinetic procedure to resolve overlapping absorbances.
• Application of the method to photochemical reactions exhibiting inner filter effects.
• Quantitative analysis of the intermolecular Si-H bond activation of (η(5)-C(5)H(5))Rh(CO)(2) in triethylsilane.

Main Results:

• The described kinetic procedure effectively measures quantum efficiencies in the presence of overlapping absorbances.
• The method accurately accounts for substantial inner filter effects.
• Successful quantitative measurement of Si-H bond activation photochemistry was achieved.

Conclusions:

• The developed kinetic method is a robust tool for determining photochemical quantum efficiencies.
• This procedure is particularly valuable for complex photochemical systems, including those involving metal complexes.
• The method has broad applicability across various photochemical investigations.