The direct synthesis of dimethyl carbonate (DMC) using carbon dioxide as solvent and reagent for its fixation to methanol was explored with di-n-butyldimethoxystannane in order to get insight into the reaction mechanism for activity improvement. Catalytic runs including recycling experiments allowed isolation and characterization by NMR, IR, and single-crystal X-ray diffraction of a new tin complex containing 10 tin atoms. This compound could be prepared independently and is considered as a resting species. The yield of DMC is highest under 20 MPa pressure that fits with a monophasic supercritical medium in agreement with fluid phase equilibria calculations. In line, preliminary kinetics and initial rate determination show a positive order in carbon dioxide and a first-order dependence on the stannane. The initial rates were lower with the deca-tin complex than with the stannane precursor, but the turnover numbers (TONs) were higher. Water, the co-product of the reaction, was found to reversibly poison the active centers. Its in situ trapping had a beneficial effect. This study provides new mechanistic clues as to the reactive species and DMC formation. Further kinetics work is in progress to determine the rate-limiting step(s) at the initial stage of the reaction for more active catalyst design. (c) 2006 Elsevier B.V. All rights reserved.