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Issue 6, 2015
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Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands

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Abstract

The synthesis and characterization of (bipy)2U(N[t-Bu]Ar)2 (1-(bipy)2, bipy = 2,2′-bipyridyl, Ar = 3,5-C6H3Me2), (bipy)U(N[1Ad]Ar)3 (2-bipy), (bipy)2U(NC[t-Bu]Mes)3 (3-(bipy)2, Mes = 2,4,6-C6H2Me3), and IU(bipy)(NC[t-Bu]Mes)3 (3-I-bipy) are reported. X-ray crystallography studies indicate that bipy coordinates as a radical anion in 1-(bipy)2 and 2-bipy, and as a neutral ligand in 3-I-bipy. In 3-(bipy)2, one of the bipy ligands is best viewed as a radical anion, the other as a neutral ligand. The electronic structure assignments are supported by NMR spectroscopy studies of exchange experiments with 4,4′-dimethyl-2,2′-bipyridyl and also by optical spectroscopy. In all complexes, uranium was assigned a +4 formal oxidation state.

Graphical abstract: Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands

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The article was received on 09 Aug 2014, accepted on 04 Dec 2014 and first published on 05 Dec 2014


Article type: Paper
DOI: 10.1039/C4DT02422B
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Citation: Dalton Trans., 2015,44, 2676-2683
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    Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands

    P. L. Diaconescu and C. C. Cummins, Dalton Trans., 2015, 44, 2676
    DOI: 10.1039/C4DT02422B

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