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

The reactivity of five di-n-butyltin(IV) complexes, n-Bu2Sn(OR)2 (1), n-Bu2SnO (3), [n-Bu2Sn(OR)]2O (4), (n-Bu2SnO)2(CO2) (6) and (n-Bu2SnO)6[(n-Bu2SnOR)2(CO3)]2 (7) (R = CH3), with CO2, suggested as possible catalyst precursors and key-intermediates for the direct synthesis of dimethyl carbonate from carbon dioxide and methanol, has been investigated using high-pressure 119Sn{1H} NMR (HP-NMR) spectroscopy. Four of the five precursors studied, i.e. 3, 4, 6 and 7 give rise to an identical 119Sn{1H} NMR pattern which can be explicitly attributed to the fingerprint of the dimeric form of the 1-methoxy-3-methylcarbonatotetrabutyldistannoxane {5}2. However, with 1, a new pair of signals is observed in addition to the characteristic 119Sn{1H} NMR resonances of the dimeric hemicarbonato species {2}2 and {5}2, which can be attributed to the in situ formation of an unprecedented species suggested to be the trinuclear carbonato di-n-butyltin(IV) complex, 8.