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Issue 18, 2018
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Chromium chains as polydentate fluoride ligands for actinides and group IV metals

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Abstract

The reactions of {Cr6} horseshoe chains {[nPr2NH2]3[Cr6F11(O2CtBu)10]}2, 1 and precursors of actinides and group IV metals led to a series of ring complexes [nPr2NH2][Cr7TiF6O2(O2CtBu)16], 2, [nPr2NH2][Cr6Ti2F5O3(O2CtBu)16], 3, [Cr6ThF7(O2CtBu)15 (Me2SO)], 4, [(nPr2NH2)2(Cr6Th2F12(O2CtBu)16)], 5 and [nPr2NH2][Cr6U2O2F8(O2CtBu)16(Me2SO)], 6. X-ray structure studies indicate that the {Cr6} chains maintain their structures in these complexes, acting as polydentate fluoride ligands. Their static magnetic properties were measured and fitted by isotropic exchange Hamiltonian. In accordance with 1, the magnetic exchanges between CrIII are antiferromagnetic, while the exchange interactions can be modified by the tetravalent metals. For compound 6, ferromagnetic exchanges JCr–U and JU–U are obtained. EPR spectra of compounds 2–5 were measured at Q band and were simulated. The spectrum of 2 has the same profile as {Cr7Cd} and {Cr7Zn} rings with a ground state S = 3/2. 3, 4 and 5 give similar EPR spectra with S = 0 ground states.

Graphical abstract: Chromium chains as polydentate fluoride ligands for actinides and group IV metals

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Publication details

The article was received on 01 Mar 2018, accepted on 28 Mar 2018 and first published on 16 Apr 2018


Article type: Paper
DOI: 10.1039/C8DT00803E
Citation: Dalton Trans., 2018,47, 6361-6369
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    Chromium chains as polydentate fluoride ligands for actinides and group IV metals

    J. Leng, A. K. Kostopoulos, L. H. Isherwood, A. Ariciu, F. Tuna, I. J. Vitórica-Yrezábal, R. G. Pritchard, G. F. S. Whitehead, G. A. Timco, D. P. Mills and R. E. P. Winpenny, Dalton Trans., 2018, 47, 6361
    DOI: 10.1039/C8DT00803E

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