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Lookup NU author(s): Balamurugan Kandasamy, Professor William Clegg, Dr Ross Harrington, Dr Magda Pascual-BorrasORCiD, Dr John ErringtonORCiD
This is the authors' accepted manuscript of an article that has been published in its final definitive form by Wiley-VCH, 2018.
For re-use rights please refer to the publisher's terms and conditions.
Incorporation of {MX}n+ groups into polyoxometalates (POMs) provides the means not only to introduce reactivity and functionality but also to tune the electronic properties of the oxide framework by varying M, X and n. In order to elucidate the factors responsible for differences in reactivity between {TiW5} and {SnW5} Lindqvist-type hexametalates, a series of alkoxido- and aryloxido-tin substituted POMs (nBu4N)3[(RO)SnW5O18] (R = Me, Et, iPr and tBu) and (nBu4N)3[(ArO)SnW5O18] (Ar = C6H5, 4-MeC6H5, 4-tBuC6H5, 4- HOC6H4, 3-HOC6H4 and 2-CHOC6H4) has been structurally characterised and studied by multinuclear NMR (1H, 13C, 17O, 119Sn and 183W) and FTIR spectroscopy. Spectroscopic and structural parameters were compared with those of titanium-substituted homologues and, when coupled with theoretical studies, indicated that Sn–OR and Sn–OAr bonds are ionic with little π-contribution, whereas Ti–OR and Ti–OAr bonds are more covalent with π- bonding that is more prevalent for Ti–OR than Ti–OAr. This experimental and theoretical analysis of bonding in a homologous series of reactive POMs is the most extensive and detailed to date, and reveals factors which account for significant differences in reactivity between tin and titanium congeners.
Author(s): Kandasamy B, Bruce PG, Clegg W, Harrington RW, Rodriguez-Fortea A, Pascual-Borras M, Errington RJ
Publication type: Article
Publication status: Published
Journal: Chemistry A European Journal
Year: 2018
Volume: 24
Issue: 11
Pages: 2750-2757
Print publication date: 21/02/2018
Online publication date: 05/01/2018
Acceptance date: 05/01/2018
Date deposited: 05/01/2018
ISSN (print): 0947-6539
ISSN (electronic): 1521-3765
Publisher: Wiley-VCH
URL: https://doi.org/10.1002/chem.201705547
DOI: 10.1002/chem.201705547
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