| Abstract | Laser flash photolysis (LFP) of di-tert-butyl peroxide or dicumyl peroxide at ambient temperatures in the presence of Et3N→BH3 or BH4- generated the title radicals which were found to have broad, featureless absorptions in the visible region. Rate constants for H-atom abstraction from Et3N→BH3 by cumyloxyl radicals show a small solvent dependence, e.g. 12 × 107 and 2.2 × 107 dm3 mol-1 s-1 in isooctane and acetonitrile, respectively. Rate constants for halogen atom abstraction by Et3N→BH2· and BH3·- from a number of chlorides and bromides were determined by LFP and by competitive kinetics, e.g., for Et3N→BH2· + CCl4/PhCH2Cl/CH3 (CH2)2Cl, k = 4.4 × 109/1.1 × 107/5.1 × 105 dm3 mol-1 s-1 and for BH3·- + CCl4/PhCH2Cl, k = 2.0 × 109/3.0 × 107 dm3 mol-1 s-1. Rates of addition of Et3N→BH2· to 1- and 1,1-substituted olefins increase dramatically as the electron affinity of the olefin increases, confirming the nucleophilic character of amine-boryl radicals. A comparison of the present results with literature data for the addition of olefins of four nucleophilic carbon-centered radicals proves that Et3N→BH2· is by far the most nucleophilic radical for which kinetic data are available. A few rate constants for abstraction of hydrogen from electron-deficient carbon by Et3N→BH2· are also reported. |
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