Triorganotin(iv) cation-promoted dimethyl carbonate synthesis from CO2 and methanol: solution and solid-state characterization of an unexpected diorganotin(iv)-oxo cluster. (2nd May 2018)

• Record Type: Journal Article
• Authors: Švec, Petr; Cattey, Hélène; Růžičková, Zdeňka; Holub, Josef; Růžička, Aleš; Plasseraud, Laurent
• Is Part Of: New journal of chemistry. Volume 42:Number 10(2018)
• Page Start: 8253
• Page End: 8260
• Publication Date: 2018-05-02
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c7nj05058e
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : Novel C, N -chelated organotin(iv ) complexes bearing weakly coordinating carborane moieties were prepared and used as a catalyst precursor for the direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol. 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. L CN R2 SnCl, R = n -Bu (1 ) and Ph (2 ); L CN = 2-( N, N -dimethylaminomethyl)phenyl)) with monocarba- closo -dodecaborate silver salt (AgCB11 H12 ; Ag·3 ). Both products of the metathesis, [L CN ( n -Bu)2 Sn] + [CB11 H12 ] − (4 ) and [L CN Ph2 Sn] + [CB11 H12 ] − (5 ), respectively, were characterized by both multinuclear NMR spectroscopy and elemental analysis. The instability of4 and5 towards water is discussed. The solid-state structure of L CN ( n -Bu)2 SnOH·B(C6 F5 )3 (4a ) as a model compound with a Sn–O(H)⋯B linkage is also reported. The evaluation of the catalytic activity of4 and5 was carried out within the direct synthesis of dimethyl carbonate (DMC) from methanol and CO2 . While5 was shown to be definitively inactive, presumably due to cleavage of the Sn–Ph bond, compound4 exhibits a beneficial action, since it leads to an amount of DMC higher than the stoichiometry ( n DMC / n Sn(cat) = 1.5). In addition, the solid state structures of [BnNMe3 ] + [CB11 H12 ] − (6 ) and [( n -Bu)20 Sn10 O2 (OMe)6 (CO3 )2 ] 2+ ·2 [CB11 H12 ] − (7 ), isolated as single-crystals and resulting from the recombination of4 under the reaction conditions (methanol/CO2 ), were established by sc-XRD analyses within the term of this work as well.6 and7 were also fully characterized by IR spectroscopy, multinuclear NMR in solution and elemental analysis.