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Bonding insights from structural and spectroscopic comparisons of {SnW5} and {TiW5} alkoxido- and aryloxido-substituted Lindqvist polyoxometalates

Lookup NU author(s): Balamurugan Kandasamy, Professor William Clegg, Dr Ross Harrington, Dr Magda Pascual-BorrasORCiD, Dr John ErringtonORCiD

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This is the authors' accepted manuscript of an article that has been published in its final definitive form by Wiley-VCH, 2018.

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Abstract

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.

Publication metadata

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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