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

Vikram Singh; Yujiao Zhang; Linping Yang; Pengtao Ma; Dongdi Zhang; Chao Zhang; Li Yu; Jingyang Niu; Jingping Wang

doi:10.3390/molecules22081351

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

Molecules. 2017 Aug 14;22(8):1351. doi: 10.3390/molecules22081351.

Authors

Vikram Singh¹, Yujiao Zhang², Linping Yang³, Pengtao Ma⁴, Dongdi Zhang⁵, Chao Zhang⁶, Li Yu⁷, Jingyang Niu⁸, Jingping Wang⁹

Affiliations

¹ Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China. singhvikram001@Gmail.com.
² Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China. unscxc@163.com.
³ Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China. linping_1986@126.com.
⁴ Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China. mpt@henu.edu.cn.
⁵ Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China. DDZhang@henu.edu.cn.
⁶ Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China. zhangchao@vip.henu.edu.cn.
⁷ Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China. yuli@henu.edu.cn.
⁸ Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China. jyniu@henu.edu.cn.
⁹ Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China. jpwang@henu.edu.cn.

Abstract

Two novel heteropolyoxomolybdate [XMo₈O₃₁]^n- (X = Ge(1) or P(2)) manganese carbonyl derivatives [(CH₃)₄N]₆H₆{Mn^II(GeMo₈O₃₁)[Mn^I(CO)₃]₂}₂·12H₂O (1) and [(CH₃)₄N]₄H₆{Mn^II(PMo₈O₃₁)[Mn^I(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 Mn^I-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 Mn^II 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.

Keywords: Keggin structure; electrocatalysts; metal tricarbonyl; polyoxomolybdates.

MeSH terms

Crystallography, X-Ray / methods
Electrochemistry / methods
Electrons
Manganese / chemistry*
Models, Molecular
Molecular Structure
Molybdenum / chemistry*
Organometallic Compounds / chemistry*
Oxygen / chemistry
Spectroscopy, Fourier Transform Infrared / methods
Thermogravimetry / methods
X-Ray Diffraction / methods

Substances

Organometallic Compounds
molybdate
Manganese
Molybdenum
Oxygen