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Molecules 2017, 22(8), 1351;

Two New Tetravacant Organometallic Keggin-Type Heteropolyoxomolybdates-Supported Manganese Carbonyl Derivatives

Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
Authors to whom correspondence should be addressed.
Received: 11 July 2017 / Revised: 9 August 2017 / Accepted: 9 August 2017 / Published: 14 August 2017
(This article belongs to the Section Organometallic Chemistry)
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Two novel heteropolyoxomolybdate [XMo8O31]n− (X = Ge(1) or P(2)) manganese carbonyl derivatives [(CH3)4N]6H6{MnII(GeMo8O31)[MnI(CO)3]2}2·12H2O (1) and [(CH3)4N]4H6{MnII(PMo8O31)[MnI(CO)3]2}2·14H2O (2), have been successfully synthesized and characterized in the solid state by single crystal X-ray diffraction, IR and thermogravimetric analysis, and in solution by UV-Vis spectroscopy and electrochemistry. The two polyoxomolybdate-based organometallic compounds 1 and 2 represent rare examples of transition metal sandwich-based polyoxometalate metal carbonyl derivatives (PMCDs), in which the organic-inorganic hybrids are composed of four Mn(CO)3+ groups symmetrically occupied the tetravacant sites of dimeric heteropolyoxomolybdate {Mn2(XMo8O31)2}n− through MnI-O-Mo bonds. The carbonyl functionalized Mn atoms are octahedrally coordinated via three μ2-oxygens of the [XMo8O31]n− unit and three carbonyl carbon atoms. Interestingly, 1 and 2 form a psedocuboidal ring Mn(CO)3Mo3O12 with {Mn(CO)3}+ occupying the three fold axis of the Mo3O12 octahedral triad. Beside this, the two centrally placed adjacent MnII atoms show intramolecular Mn∙∙∙Mn interactions of 3.11 and 3.16 Å in 1 and 2, respectively. Significant n→π* and O···O intermolecular interactions between the orthogonally aligned adjacent carbonyl groups through the overlap of lone-pair electrons on oxygen atoms with the antibonding orbital (π*) of the adjacent carbony carbon atom of the subsequent units in 1 and 2 were observed. The electrochemical properties of the two compounds were also been investigated. View Full-Text
Keywords: polyoxomolybdates; metal tricarbonyl; electrocatalysts; Keggin structure polyoxomolybdates; metal tricarbonyl; electrocatalysts; Keggin structure

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Singh, V.; Zhang, Y.; Yang, L.; Ma, P.; Zhang, D.; Zhang, C.; Yu, L.; Niu, J.; Wang, J. Two New Tetravacant Organometallic Keggin-Type Heteropolyoxomolybdates-Supported Manganese Carbonyl Derivatives. Molecules 2017, 22, 1351.

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