Hydroxo radicals, C-H activation, and Pt-C bond formation from 77 K photolysis of a platinum(IV) hydroxo complex.

Inorg Chem

Department of Chemistry, University of Missouri, 125 Chemistry Building, Columbia, Missouri 65211-7600, United States.

Published: November 2014

Photolysis (380 nm) of trans,cis-Pt(PEt3)2(Cl)2(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 trans-Pt(CH2CH2PEt2)(PEt3)(Cl)2(4-tft) by hydrogen-atom abstraction from a PEt3 ligand and trans-Pt(PEt3)2(Cl)(4-tft) from net HOCl photoelimination. The platinacycle undergoes thermal reductive elimination at 298 K or photolytic reductive elimination, even at 77 K.

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http://dx.doi.org/10.1021/ic502325rDOI Listing

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