Dichotomous hydrogen atom transfer vs proton-coupled electron transfer during activation of X-H bonds (X = C, N, O) by nonheme iron-oxo complexes of variable basicity.

ABSTRACT: We describe herein the hydrogen-atom transfer (HAT)/proton-coupled electron-transfer (PCET) reactivity for Fe(IV)-oxo and Fe(III)-oxo complexes (1-4) that activate C-H, N-H, and O-H bonds in 9,10-dihydroanthracene (S1), dimethylformamide (S2), 1,2-diphenylhydrazine (S3), p-methoxyphenol (S4), and 1,4-cyclohexadiene (S5). In 1-3, the iron is pentacoordinated by tris[N'-tert-butylureaylato)-N-ethylene]aminato ([H3buea](3-)) or its derivatives. These complexes are basic, in the order 3 ≫ 1 > 2. Oxidant 4, [Fe(IV)N4Py(O)](2+) (N4Py: N,N-bis(2-pyridylmethyl)bis(2-pyridyl)methylamine), is the least basic oxidant. The DFT results match experimental trends and exhibit a mechanistic spectrum ranging from concerted HAT and PCET reactions to concerted-asynchronous proton transfer (PT)/electron transf

SUBMITTER: Usharani D 

PROVIDER: S-EPMC3876471 | biostudies-literature | 2013 Nov

REPOSITORIES: biostudies-literature