Hydroxo Radicals, C–H Activation, and Pt–C
Bond Formation from 77 K Photolysis of a Platinum(IV) Hydroxo Complex
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Abstract
Photolysis
(380 nm) of <i>trans</i>,<i>cis</i>-Pt(PEt<sub>3</sub>)<sub>2</sub>(Cl)<sub>2</sub>(OH)(4-tft) (4-tft
= 4-trifluoromethylphenyl) at 77 K in 2-methyltetrahydrofuran gives
triplet emission, platinum(III), and a hydroxo radical. Benzyl radical
emission is observed in toluene from the reaction of a portion of
the OH radicals with toluene. Warming the photolyzed solutions gives
platinacycle <i>trans</i>-Pt(CH<sub>2</sub>CH<sub>2</sub>PEt<sub>2</sub>)(PEt<sub>3</sub>)(Cl)<sub>2</sub>(4-tft) by hydrogen-atom
abstraction from a PEt<sub>3</sub> ligand and <i>trans</i>-Pt(PEt<sub>3</sub>)<sub>2</sub>(Cl)(4-tft) from net HOCl photoelimination.
The platinacycle undergoes thermal reductive elimination at 298 K
or photolytic reductive elimination, even at 77 K
