Ligand Topology Effect on the Reactivity of a Mononuclear Nonheme Iron(IV)-Oxo Complex in Oxygenation Reactions

다국어 초록 (Multilingual Abstract)

<P>Mononuclear nonheme iron(IV)-oxo complexes with two different topologies, <I>cis</I>-α-[Fe<SUP>IV</SUP>(O)(BQCN)]<SUP>2+</SUP> and <I>cis</I>-β-[Fe<SUP>IV</SUP>(O)(BQCN)]<SUP>2+</SUP>, were synthesized and characterized with various spectroscopic methods. The effect of ligand topology on the reactivities of nonheme iron(IV)-oxo complexes was investigated in C–H bond activation and oxygen atom-transfer reactions; <I>cis</I>-α-[Fe<SUP>IV</SUP>(O)(BQCN)]<SUP>2+</SUP> was more reactive than <I>cis</I>-β-[Fe<SUP>IV</SUP>(O)(BQCN)]<SUP>2+</SUP> in the oxidation reactions. The reactivity difference between the <I>cis</I>-α and <I>cis</I>-β isomers of [Fe<SUP>IV</SUP>(O)(BQCN)]<SUP>2+</SUP> was rationalized with the Fe<SUP>IV/III</SUP> redox potentials of the iron(IV)-oxo complexes: the Fe<SUP>IV/III</SUP> redox potential of the <I>cis</I>-α isomer was 0.11 V higher than that of the <I>cis</I>-β isomer.</P><P><B>Graphic Abstract</B>
<IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2011/jacsat.2011.133.issue-31/ja204008u/production/images/medium/ja-2011-04008u_0004.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja204008u'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja204008u'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja204008u'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja204008u'>ACS Electronic Supporting Info</A></P>