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POM-FLPs: [MoIV3]n-Polyoxometalate Bifunctional Catalysis by [MoIV3]n-Om Lewis Pairs Frustrated by Triangular MoIV-MoIV Bonds


Lewis acid and Lewis base pairs combined in a single system is emerging as one of the most active frontiers areas in bifunctional catalysis. To serve as efficient Lewis acid Lewis base bifunctional catalysts, more reduced MoIVn-polyoxometalates having multiple MoIV-(μ2-O) Lewis pairs are necessary. The new mixed solvent pyridine/DMF/H2O and heterometal oxide (GeO2) have been introduced to the solvothermal partial oxidation system of [Mo3O2(O2CCH3)6(H2O)3]ZnCl4 to yield the two novel [MoIV3]n-POMs family members: the largest H4[Mo@MoIV6MoV6MoVI8O54(OH)4py6] ({Mo@Mo20}-1) and the first example incorporating group IV metals H[Ge@MoIV6MoVI10Zn0.5Ge1.5O48py6] ({Ge@Mo16Ge1.5Zn0.5}-2), providing two new important routes to extend POM-FLPs system and allowing for a systematic investigation into their reasonable syntheses, diversified molecular and electronic structures, and their influence on the catalytic efficiency. The POM-FLPs system exhibits excellent selectivity (>97%) and structure-dependent conversion dominated by the HOMO MoIV percentage, the number and linkage of [MoIV3]n-(μ2-O)m FLPs in hydrazine transfer hydrogenation reduction of nitrobenzene to aniline, which is helpful to guide target synthesis and optimal performance of POM-FLPs in catalysing hydrogenation or other reactions that are to be developed.

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Publication details

The article was received on 06 Mar 2019, accepted on 15 Apr 2019 and first published on 16 Apr 2019

Article type: Paper
DOI: 10.1039/C9DT00983C
Citation: Dalton Trans., 2019, Accepted Manuscript

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    POM-FLPs: [MoIV3]n-Polyoxometalate Bifunctional Catalysis by [MoIV3]n-Om Lewis Pairs Frustrated by Triangular MoIV-MoIV Bonds

    B. Luo and L. Xu, Dalton Trans., 2019, Accepted Manuscript , DOI: 10.1039/C9DT00983C

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