Toggle Main Menu Toggle Search

Open Access padlockePrints

Why does Nb(V) show higher heterolytic pathway selectivity than Ti(IV) in epoxidation with H2O2? Answers from model studies on Nb- and Ti-substituted Lindqvist tungstates

Lookup NU author(s): Dr Nataliya Maksimchuk, Daniel Lebbie, Dr John ErringtonORCiD



This is the authors' accepted manuscript of an article that has been published in its final definitive form by American Chemical Society, 2019.

For re-use rights please refer to the publisher's terms and conditions.


Ti- and Nb-monosubstituted tungstates of the Lindqvist structure, (Bu4N)3[(CH3O)TiW5O18] (TiW5) and (Bu4N)2[(CH3O)NbW5O18] (NbW5), display catalytic reactivity analogous to that of heterogeneous Ti- and Nb-containing catalysts in alkene oxidation with aqueous hydrogen peroxide. In this work, we make an attempt to rationalize the differences observed in the catalytic performance of Ti and Nb single site catalysts for alkene epoxidation with H2O2 using MW5 (M = Ti and Nb) as tractable molecular models. In the oxidation of cyclohexene, NbW5 reveals higher catalytic activity and heterolytic pathway selectivity than its Ti counterpart while TiW5 is more active for decomposition of H2O2. The heterolytic and homolytic oxidation pathways have been investigated by means of kinetic and computational tools. The kinetic trends established for MW5-catalyzed epoxidation, comparative spectroscopic studies (IR, Raman, UV-vis, and 1H and 17O NMR) of the reaction between MW5 and hydrogen peroxide, and DFT calculations implemented on cyclohexene epoxidation over MW5 strongly support a mechanism that involves interaction of either MW5 or its hydrolyzed form ‘MOH’ with Н2О2 to afford a protonated peroxo species ‘HMO2’ that is present in equilibrium with a hydroperoxo species ‘MOOH’, followed by electrophilic oxygen atom transfer from ‘MOOH’ to the С=С bond to give epoxide and ‘MOH’. For both Ti and Nb, the peroxo species ‘HMO2’ is more stable than the hydroperoxo species ‘MOOH’ but the latter is more reactive toward alkenes. For Ti catalyst, which has a rigid and hindered metal center, the hydroperoxo species transfers preferentially the nondistorted -oxygen whereas for the Nb catalysts the transference of the more electrophilic -oxygen is favored. Moreover, upon increasing the oxidation state from Ti(IV) to Nb(V) the reaction accelerates and selectivity towards electrophilic products increases. Calculations showed that the Nb(V) catalyst reduces significantly the free-energy barrier for the heterolytic oxygen transfer because of the higher electrophilicity of the metal center. The improved performance of the Nb(V) single-site is due to a combination of a flexible coordination environment with a higher metal oxidation state.

Publication metadata

Author(s): Maksimchuk NV, Ivanchikova ID, Maksimov GM, Eltsov IV, Evtushok VY, Kholdeeva OA, Lebbie D, Errington RJ, Solé-Daura A, Poblet JM, Carbó JJ

Publication type: Article

Publication status: Published

Journal: ACS Catalysis

Year: 2019

Volume: 9

Pages: 6262-6275

Print publication date: 14/06/2019

Online publication date: 30/05/2019

Acceptance date: 04/05/2019

Date deposited: 30/05/2019

ISSN (electronic): 2155-5435

Publisher: American Chemical Society


DOI: 10.1021/acscatal.9b01326


Altmetrics provided by Altmetric


Funder referenceFunder name