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The slow reaction of [CoIII(apPh)2]−with PhCH2X likely further highlights the sensitivity of the reaction to steric hindrance.
Reactions with haloalkanes that are probes of radical intermediates (e.g., (bromomethyl)cyclopropane) were inconclusive because the1H NMR spectrum of the organometallic alkylcobalt(III) products are broadened by trace quantities of theS=1/2CoIII(apAr)(isqAr) decomposition product.
The speciation of reduced cobalt complex is concentration dependent. [CoIII(apPh)2]−reacts rapidly with PhZnBr to form an equilibrium adduct that we tentatively formulate as [CoIII(Ph)(apPh)2]2−.
In both reactions the balance of the cobalt-derived ethyls was not found. These may form butane, which is not quantitated by the GC-MS method used.
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