Triorganotin(iv) cation-promoted dimethyl carbonate synthesis from COinf2/infand methanol: Solution and solid-state characterization of an unexpected diorganotin(iv)-oxo cluster

0489916 - ÚACH 2019 RIV GB eng J - Článek v odborném periodiku
Švec, P. - Cattey, H. - Růžičková, Z. - Holub, Josef - Růžička, A. - Plasseraud, L.
Triorganotin(iv) cation-promoted dimethyl carbonate synthesis from COinf2/infand methanol: Solution and solid-state characterization of an unexpected diorganotin(iv)-oxo cluster.
New Journal of Chemistry. Roč. 42, č. 10 (2018), s. 8253-8260. ISSN 1144-0546. E-ISSN 1369-9261
Grant CEP: GA ČR(CZ) GA16-01618S
Institucionální podpora: RVO:61388980
Klíčová slova: carbon dioxide * carbonic acid derivative * cation * methanol * methyl group * organotin compound
Obor OECD: Inorganic and nuclear chemistry
Impakt faktor: 3.069, rok: 2018

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 R 2 SnCl, R = n-Bu (1) and Ph (2),, L CN = 2-(N,N-dimethylaminomethyl)phenyl)) with monocarba-closo-dodecaborate silver salt (AgCB 11 H 12 , Ag·3). Both products of the metathesis, [L CN (n-Bu) 2 Sn] + [CB 11 H 12 ] (4) and [L CN Ph 2 Sn] + [CB 11 H 12 ] (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 L CN (n-Bu) 2 SnOH·B(C 6 F 5 ) 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 CO 2 . 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 (n DMC /n Sn(cat) = 1.5). In addition, the solid state structures of [BnNMe 3 ] + [CB 11 H 12 ] (6) and [(n-Bu) 20 Sn 10 O 2 (OMe) 6 (CO 3 ) 2 ] 2+ ·2[CB 11 H 12 ] (7), isolated as single-crystals and resulting from the recombination of 4 under the reaction conditions (methanol/CO 2 ), 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.
Trvalý link: http://hdl.handle.net/11104/0284891


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