Triorganotin(iv) cation-promoted dimethyl carbonate synthesis from CO<inf>2</inf>and methanol: Solution and solid-state characterization of an unexpected diorganotin(iv)-oxo cluster

Kód výsledku v IS VaVaI

RIV/61388980:_____/18:00489916 - isvavai.cz

Výsledek na webu

http://dx.doi.org/10.1039/c7nj05058e

DOI - Digital Object Identifier

10.1039/c7nj05058e

Jazyk výsledku

angličtina

Název v původním jazyce

Triorganotin(iv) cation-promoted dimethyl carbonate synthesis from CO2and methanol: Solution and solid-state characterization of an unexpected diorganotin(iv)-oxo cluster

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Triorganotin(iv) cation-promoted dimethyl carbonate synthesis from CO2and methanol: Solution and solid-state characterization of an unexpected diorganotin(iv)-oxo cluster

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

GA16-01618S: Desetivrcholové dikarbaboranové molekulární útvary vytvořené alkylací

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2018

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

New Journal of Chemistry

ISSN

1144-0546

e-ISSN

—

Svazek periodika

42

Číslo periodika v rámci svazku

10

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

8

Strana od-do

8253-8260

Kód UT WoS článku

000434245500080

EID výsledku v databázi Scopus

2-s2.0-85047020582