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Issue 44, 2011
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Synthesis and characterization of oxorhenium(V) diamido pyridine complexes that catalyze oxygen atom transfer reactions

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Abstract

The detailed syntheses of complexes 1–4, Re(O)(X)(DAP) (X = Me, 1; Cl, 2; I, 3; OTf (triflate), 4) incorporating the diamido pyridine (DAP) ancillary ligand (2,6-bis((mesitylamino)methyl)pyridine) are described and shown to be effective catalysts for oxygen atom transfer (OAT) reactions of PyO to PPh3. The catalytic activities are as follows: 43 > 2 > 1. The observed electronic trend is consistent with the turnover limiting reduction of the proposed Re(VII) dioxo intermediate, Re(O)2(X)(DAP), during the catalytic cycle. The catalytic activity of complexes 1–3 was compared to previously published diamido amine (DAAm) oxorhenium complexes of the type Re(O)(X)(DAAm) (X = Me, 5; Cl, 6; I, 7 and DAAm = N,N-bis(2-arylaminoethyl)methylamine) which exhibit hydrolytic degradation during the catalytic reaction. Complexes 1–3 displayed higher turnover frequencies compared to 5–7. This higher catalytic activity was attributed to the more rigid DAP ligand backbone, which makes the complexes less susceptible to decomposition. However, another decomposition pathway was proposed for this catalytic system due to the observation of Re(O)3((MesNCH2)(MesNCH)NC5H3) 8 in which one arm of the DAP ligand is oxidized.

Graphical abstract: Synthesis and characterization of oxorhenium(v) diamido pyridine complexes that catalyze oxygen atom transfer reactions

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Publication details

The article was received on 17 Jun 2011, accepted on 15 Aug 2011 and first published on 04 Oct 2011


Article type: Paper
DOI: 10.1039/C1DT11143D
Citation: Dalton Trans., 2011,40, 11815-11821
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    Synthesis and characterization of oxorhenium(V) diamido pyridine complexes that catalyze oxygen atom transfer reactions

    C. P. Lilly, P. D. Boyle and E. A. Ison, Dalton Trans., 2011, 40, 11815
    DOI: 10.1039/C1DT11143D

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