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Issue 46, 2012
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Structural and reactivity comparison of analogous organometallic Pd(III) and Pd(IV) complexes

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Abstract

The tetradentate ligands RN4 (RN4 = N,N′-di-alkyl-2,11-diaza[3,3](2,6)pyridinophane, R = Me or iPr) were found to stabilize cationic (RN4)PdMe2 and (RN4)PdMeCl complexes in both PdIII and PdIV oxidation states. This allows for the first time a direct structural and reactivity comparison of the two Pd oxidation states in an identical ligand environment. The PdIII complexes exhibit a distorted octahedral geometry, as expected for a d7 metal center, and display unselective C–C and C–Cl bond formation reactivity. By contrast, the PdIV complexes have a pseudo-octahedral geometry and undergo selective non-radical C–C or C–Cl bond formation that is controlled by the ability of the complex to access a five-coordinate intermediate.

Graphical abstract: Structural and reactivity comparison of analogous organometallic Pd(iii) and Pd(iv) complexes

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Publication details

The article was received on 14 Sep 2012, accepted on 03 Oct 2012 and first published on 04 Oct 2012


Article type: Communication
DOI: 10.1039/C2DT32127K
Citation: Dalton Trans., 2012,41, 14046-14050
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    Structural and reactivity comparison of analogous organometallic Pd(III) and Pd(IV) complexes

    F. Tang, F. Qu, J. R. Khusnutdinova, N. P. Rath and L. M. Mirica, Dalton Trans., 2012, 41, 14046
    DOI: 10.1039/C2DT32127K

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