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Issue 10, 2018
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Triorganotin(IV) cation-promoted dimethyl carbonate synthesis from CO2 and methanol: solution and solid-state characterization of an unexpected diorganotin(IV)-oxo cluster

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Abstract

Two novel C,N-chelated organotin(IV) complexes bearing weakly coordinating carborane moieties were prepared by the reaction of the corresponding C,N-chelated organotin(IV) chloride (i.e. LCNR2SnCl, R = n-Bu (1) and Ph (2); LCN = 2-(N,N-dimethylaminomethyl)phenyl)) with monocarba-closo-dodecaborate silver salt (AgCB11H12; Ag·3). Both products of the metathesis, [LCN(n-Bu)2Sn]+[CB11H12] (4) and [LCNPh2Sn]+ [CB11H12] (5), respectively, were characterized by both multinuclear NMR spectroscopy and elemental analysis. The instability of 4 and 5 towards water is discussed. The solid-state structure of LCN(n-Bu)2SnOH·B(C6F5)3 (4a) as a model compound with a Sn–O(H)⋯B linkage is also reported. The evaluation of the catalytic activity of 4 and 5 was carried out within the direct synthesis of dimethyl carbonate (DMC) from methanol and CO2. While 5 was shown to be definitively inactive, presumably due to cleavage of the Sn–Ph bond, compound 4 exhibits a beneficial action, since it leads to an amount of DMC higher than the stoichiometry (nDMC/nSn(cat) = 1.5). In addition, the solid state structures of [BnNMe3]+[CB11H12] (6) and [(n-Bu)20Sn10O2(OMe)6(CO3)2]2+·2[CB11H12] (7), isolated as single-crystals and resulting from the recombination of 4 under the reaction conditions (methanol/CO2), were established by sc-XRD analyses within the term of this work as well. 6 and 7 were also fully characterized by IR spectroscopy, multinuclear NMR in solution and elemental analysis.

Graphical abstract: Triorganotin(iv) cation-promoted dimethyl carbonate synthesis from CO2 and methanol: solution and solid-state characterization of an unexpected diorganotin(iv)-oxo cluster

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Publication details

The article was received on 20 Dec 2017, accepted on 23 Apr 2018 and first published on 23 Apr 2018


Article type: Paper
DOI: 10.1039/C7NJ05058E
Citation: New J. Chem., 2018,42, 8253-8260
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    Triorganotin(IV) cation-promoted dimethyl carbonate synthesis from CO2 and methanol: solution and solid-state characterization of an unexpected diorganotin(IV)-oxo cluster

    P. Švec, H. Cattey, Z. Růžičková, J. Holub, A. Růžička and L. Plasseraud, New J. Chem., 2018, 42, 8253
    DOI: 10.1039/C7NJ05058E

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