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Oxygen atom transfer with organofunctionalized polyoxovanadium clusters: O-atom vacancy formation with tertiary phosphanes and deoxygenation of styrene oxide

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Abstract

We report a rare example of oxygen atom transfer (OAT) from a polyoxometalate cluster to a series of tertiary phosphanes. Addition of PR3 (PR3 = PMe3, PMe2Ph, PMePh2, PPh3) to a neutral methoxide-bridged polyoxovanadate-alkoxide (POV-alkoxide) cluster, [V6O7(OMe)12]0, results in isolation of a reduced structure with phosphine oxide datively coordinated to a site-differentiated VIII ion. A positive correlation between the steric and electronic properties of the phosphane and the reaction rate was observed. Further investigation of the steric influence of the alkoxy-bridged clusters on OAT was probed through the use of POV clusters with bridging alkoxide ligands of varying chain length ([V6O7(OR′)12]; R′ = Et, nPr). These investigations expose that steric hinderance of the vanadyl moieties has significant influence on the rate of OAT. Finally, we report the reactivity of the reduced POV-alkoxide clusters with styrene oxide, resulting in the deoxygenation of the substrate to generate styrene. This result is the first example of epoxide deoxygenation using homometallic polyoxometalate clusters, demonstrating the potential for mono-vacant Lindqvist clusters to catalyze the removal of oxygen atoms from organic substrates.

Graphical abstract: Oxygen atom transfer with organofunctionalized polyoxovanadium clusters: O-atom vacancy formation with tertiary phosphanes and deoxygenation of styrene oxide

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Publication details

The article was received on 12 Jun 2019, accepted on 13 Jul 2019 and first published on 15 Jul 2019


Article type: Edge Article
DOI: 10.1039/C9SC02882J
Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY license
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    Oxygen atom transfer with organofunctionalized polyoxovanadium clusters: O-atom vacancy formation with tertiary phosphanes and deoxygenation of styrene oxide

    B. E. Petel, R. L. Meyer, W. W. Brennessel and E. M. Matson, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C9SC02882J

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