Vladimir Jakubek, PharmAssist Analytical Laboratory, Inc., South New Berlin, NY and Alistair J. Lees, SUNY at Binghamton, Binghamton, NY.
The quantitative photochemistry of the platinum organometallic complex, Cp'Pt(CH3)3 (Cp' = η5-C5H4CH3), has been investigated in various solvents at 293 K following UV irradiation into the lowest lying absorption bands. An efficient photochemical disappearance of the parent complex was determined in n-pentane and in methylcyclohexane solutions. The comparison of absolute photochemical quantum efficiency (Φcr) results obtained for Cp'Pt(CH3)3 at 313 and 366 nm in these solvents (Φcr = 0.34-0.41) and when 53 mM Et3SiH is incorporated (Φcr = 0.79-0.85) reveals that the system undergoes even more effective photoreactions upon presence of Si-H groups. These photoefficiencies indicate that the quantitative photochemistry is higher than previously recognized (by 2 orders of magnitude). Moreover, this highly efficient photoinitiation reaction has been demonstrated in the application of Cp'Pt(CH3)3 as an effective photoinitiator for hydrosilylation reactions involving vinyl/hydride silicone mixtures.
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