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| - Ultrafast Dynamics of Cp*M(CO)2 (M = Ir, Rh) in Solution: The Origin of the Low Quantum Yields for C−H BondActivation
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| - Using picosecond transient absorption spectroscopy we haveexamined the dynamics of Cp*Ir(CO)2 (Cp*= C5Me5) in cyclohexane andCp*Rh(CO)2 in n-pentane solution at roomtemperature following 295-nm UV excitation.A transient absorption with an instrument limited risetime wasobserved for Ir from 440 to 740 nm and for Rh from500 to 650 nm. Each transient can be well fit to a biexponentialdecay consisting of a fast component of 2−3 ps anda slower component of 30−40 ps. These transients are attributedto excited state absorptions. Taking into accountindependent femtosecond IR studies of the ground state recovery and ourdata, we suggest that most excited statemolecules relax through nondissociative excited states, decaying to theground state without the loss of CO. Theseresults offer an explanation for the low C−H bond activation quantumyields observed on preparative irradiation ofCp*Ir(CO)2 andCp*Rh(CO)2.
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