Dataset Information

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

ABSTRACT: Two novel heteropolyoxomolybdate [XMo?O₃₁]^n- (X = Ge(1) or P(2)) manganese carbonyl derivatives [(CH?)?N]?H?{Mn^II(GeMo?O₃₁)[Mn^I(CO)?]?}?·12H?O (1) and [(CH?)?N]?H?{Mn^II(PMo?O₃₁)[Mn^I(CO)?]?}?·14H?O (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)?? groups symmetrically occupied the tetravacant sites of dimeric heteropolyoxomolybdate {Mn?(XMo?O₃₁)?}^n- through Mn^I-O-Mo bonds. The carbonyl functionalized Mn atoms are octahedrally coordinated via three ??-oxygens of the [XMo?O₃₁]^n- unit and three carbonyl carbon atoms. Interestingly, 1 and 2 form a psedocuboidal ring Mn(CO)?Mo?O₁₂ with {Mn(CO)?}? occupying the three fold axis of the Mo?O₁₂ 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??* 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 (?*) 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.

SUBMITTER: Singh V

PROVIDER: S-EPMC6152162 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

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

Singh Vikram V Zhang Yujiao Y Yang Linping L Ma Pengtao P Zhang Dongdi D Zhang Chao C Yu Li L Niu Jingyang J Wang Jingping J

Molecules (Basel, Switzerland) 20170814 8

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 ...[more]

PMID: 28805742

Similar Datasets

Project description:A new hybrid inorganic-organometallic salt has been obtained from the reaction of the Keggin-type silicotungstate anion with ferrocene in a water/methanol mixture as a result of the partial oxidation of ferrocene molecules to ferrocenium cations. Single-crystal X-ray diffraction analysis reveals the presence of four ferrocenium (FeIII) cations and one ferrocene (FeII) molecule per plenary Keggin anion in the crystal structure of [FeIII (Cp)?]?[SiW12O40]·[FeII(Cp)?]·2CH?OH (1). Compound 1 thus constitutes the first example in the literature in which ferrocenium and ferrocene species coexist in the structure of a polyoxometalate-based salt. The two crystallographically independent ferrocenium species in the asymmetric unit of 1 exhibit different configurations: One displays an eclipsed conformation with ideal D5h symmetry, whereas the conformation in the other one is staggered D5d. The crystal packing of 1 can be best described as an organometallic sub-lattice of ferrocenium and ferrocene species linked by a network of ?-? interactions that generates rectangular cavities of about 14 × 10 Å in which strings of Keggin anions and methanol molecules are hosted, further connected to each other via weak OPOM···CMeOH-OMeOH···OPOM type hydrogen bonds. The charge-transfer nature of the salt has been studied by solid-state diffuse reflectance UV-Vis spectroscopy and the presence of magnetically isolated FeIII/FeII centres has been confirmed by Mössbauer spectroscopy. A topological study carried out on all of the pristine ferrocenyl species deposited in the Cambridge Structural Database (CSD) has allowed two main conclusions to be drawn: (1) these species tend to adopt extreme conformations (either eclipsed or staggered) with less than a 15% of examples showing intermediate states and (2) the oxidation state of the iron centres can be unequivocally assigned on the basis of a close inspection of the Fe···Cp distances, which allows ferrocene neutral molecules and ferrocenium cations to be easily distinguished.

Dataset Information

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

Publications

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

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure