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Issue 17, 2004
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On, off and intermediate coordination of a bridgehead triarylamine donor in tripodal complexes: Towards the tuning of coordinative bond distance

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Abstract

A series of first row transition metal complexes of the tripodal ligand 2,2′,2″-nitrilotribenzoic acid H3333L has been prepared and characterised by X-ray crystallography: Mononuclear [M(L)] species [Cu(H2O)4]3[Cu(L)(H2O)]6·25H2O (2), [Co(H2O)6][Co(L)(H2O)]·8H2O (4), [Zn(H2O)6] [Zn(L)(H2O)]·8H2O (5) and a neutral [M(L)] complex [FeIII(L)(H2O)3]·5H2O (8) are formed as well as dimeric [M(L)]22− species (HNEt3)2[Cu(L)]2·2CH3CN (1), (HNEt3)3[Ni(L)]2(ClO4)·H2O (3), (HNEt3)2[FeII(L)]2·2CH3CN (6) and (HNEt3)2[FeIII2(L)2(μ-O)] (7). The complexes display a unique variation in the M–N distance (2.09 Å for CuII to 3.29 Å for FeIII) to the bridgehead triphenylamine donor and are classified into compounds with “On”,”Off” and “Intermediate” N-coordination. The trigonal-bipyramidal coordination polyhedron changes towards tetrahedral in the intermediate and octahedral in the Off-state. The M–N distance of individual complexes is reversibly tuned by external chemical input such as changes of metal ion oxidation state (FeII/FeIII) or variation of the axial coligand as a consequence of solvent or pH variation. Possible reasons for the exceptional tolerance of the M–N bond to distance variations are discussed under consideration of gas phase DFT calculations of [Zn(L)].

Graphical abstract: On, off and intermediate coordination of a bridgehead triarylamine donor in tripodal complexes: Towards the tuning of coordinative bond distance

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Publication details

The article was received on 04 May 2004, accepted on 17 Jun 2004 and first published on 28 Jul 2004


Article type: Paper
DOI: 10.1039/B406682K
Citation: Dalton Trans., 2004,0, 2750-2757
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    On, off and intermediate coordination of a bridgehead triarylamine donor in tripodal complexes: Towards the tuning of coordinative bond distance

    S. Wörl, D. Hellwinkel, H. Pritzkow, M. Hofmann and R. Krämer, Dalton Trans., 2004, 0, 2750
    DOI: 10.1039/B406682K

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