Di-n-butyltin(IV)-catalyzed dimethyl carbonate synthesis from carbon dioxide and methanol: An in situ high pressure 119Sn{1H} NMR spectroscopic study

Recent advances in dialkyl carbonates synthesis and applications

“…[145][146][147] Various characterizations were applied to provide insight into the structure of the postulated complex and intermediate species under catalytic conditions, and carbonate complexes formed by CO 2 insertion into the Sn-O bond were proposed as a key intermediate. [148][149][150][151][152][153] Acidic and basic components are utilized as promoters when using organic metal alkoxide catalysts. Sakakura and co-workers discovered that the addition of a small amount of triflate salt to Bu 2 SnO or Ti(O-i-Pr) 4 -based catalysts provided a remarkably enhanced productivity.…”

Dimethyl Carbonate Synthesis from CO2 and Dimethoxytin(IV) Complexes: The Anatomy of the Alkylation Step Viewed from DFT Modeling

“…It turned out to be active for DMC synthesis at 423 K and 20 MPa CO 2 in methanol as solvent. Under the same conditions, complex 7 was previously isolated and characterized after the reaction with the analog tert -Bu 2 Sn­(OCH 3 ) 2 , and its 119 Sn­{ 1 H} NMR signature detected by in situ high-pressure experiments in the n -butyl series . In summary, reaction profiles suggested by the DFT calculations are supported by the experimental characterization of complexes.…”

“…Under the same conditions, complex 7 was previously isolated and characterized after the reaction with the analog tert-Bu 2 Sn(OCH 3 ) 2 , 45 and its 119 Sn{ 1 H} NMR signature detected by in situ high-pressure experiments in the n-butyl series. 46 In summary, reaction profiles suggested by the DFT calculations are supported by the experimental characterization of complexes. Moreover, Schemes 3 and 4 point out species 4 to be a key intermediate in the catalytic cycle to give back the active stannane 1 in methanol.…”

Organic Carbonates

“…Both physical and chemical water traps have been employed to that end with varying success, and the effect of water traps is discussed later. 8 Water is suggested to interfere with these catalyst intermediates, limiting the yield to approximately 1 molecule DMC/Sn. The catalyzing ability of tin oxides for the carboxylation of methanol has been known since the mid-1970s, but this system has been thoroughly reinvestigated since about the turn of the century by several groups, particularly Kizlink in the early 1990s, followed by those of Sakakura and Ballivet-Tkatchenko.…”