Reactivity of di-tert-butyldimethoxystannane with carbon dioxide and methanol: X-ray structure of the resulting complex

2006

Abstract The synthesis of dimethyl carbonate from carbon dioxide and methanol was studied with ditert-butyldimethoxystannane under pressure at temperatures ⩽423 K. The formation of dimethyl carbonate is accompanied by transformation of the stannane into a trinuclear complex, the structure of which has been determined by single-crystal X-ray diffraction technique. The relevance of this specie in the catalytic cycle is demonstrated by conducting recycling runs. A preliminary kinetic study underlines the steric influence of the tert-butyl ancillary ligands in the stabilisation of intermediates, by comparison with the n-butyl homologue.

Synthesis of dimethyl carbonate in supercritical carbon dioxide

2006

The reactivity of carbon dioxide with methanol to form dimethyl carbonate was studied in the presence of the n-butylmethoxytin compounds n-Bu3SnOCH3, n-Bu2Sn(OCH3)2 , and [n-Bu2(CH3O)Sn]2 O. The reaction occurred under solventless conditions at 423 K and was produced by an increase in CO2 pressure. This beneficial effect is primarily attributed to phase behavior. The mass transfer under liquid-vapor biphasic conditions was not limiting when the system reached the supercritical state for a CO2 pressure higher than 16 MPa. Under these conditions, CO2 acted as a reactant and a solvent.

Gas-Phase Hydrogenation of Propionitrile Catalyzed by LnCu2 (Ln = La, Ce, Pr, Nd)

2007

The hydrogenation of propionitrile over binary copper−lanthanide intermetallic compounds (LnCu2, Ln = La, Ce, Pr, Nd) was studied in the gas phase. The results show that the reaction main product is the primary amine, the n-propylamine. To our knowledge, it is the first time that such behavior is reported for copper catalysts.

Synthesis of Linear and Cyclic Carbonates

2010

CO2 as a C1-Building Block for Dialkyl Carbonate Synthesis

2002

Carbon dioxide, one of the major man-made greenhouse gas, is a renewable resource of carbon which can be viewed as a C1 synthon to build valuable chemicals. The development of new applications is of major interest considering CO2 conversion and environmentally friendly reactions. As chemical catalysis offers interesting options, we are studying the molecular design of catalysts for the formation of dialkyl carbonates from alcohols and CO2. This paper reports results on the mechanistic approach for dialkyl carbonate formation with alkoxybutyl tin(IV) compounds. The insertion of CO2 into Sn-OR bonds (R = Me, 1Pr) occurs at atmospheric pressure and room temperature leading to alkylcarbonato ti…

Gas-phase hydrogenation of propionitrile on copper-lanthanide oxides

2009

Abstract The hydrogenation of propionitrile on copper-lanthanide oxide catalysts (2Cu·CeO 2 and 4Cu·Ln 2 O 3 (Ln = La, Pr, Nd)) was studied in the gas phase. The activity of the catalysts varies with the lanthanide in the order 2Cu·CeO 2  > 4Cu·Pr 2 O 3  > 4Cu·La 2 O 3  ≥ 4Cu·Nd 2 O 3 , while the activation energies varies in the opposite order, except for 2Cu·CeO 2 . The main product was the primary amine, n -propylamine. The formation of the unstable imine CH 3 CH 2 N CHCH 3 as a major product over 2Cu·CeO 2 seems to be consistent with the acidity of the catalyst. The catalysts were more selective than conventional copper impregnation catalysts, Cu (10 wt.%) on SiO 2 , La 2 O 3 or CeO 2 ,…

Linear Organic Carbonates

2003

The most common and successful method for producing organic carbonates, including polycarbonates, has been based for long time on the reaction between an alcohol or phenol and phosgene. The existing strict environmental regulations and the expanding market for organic carbonates do not assure that this technology can continue to have a leading role in this area, due to the inherent riskfulness of the processes. The market expansion of dimethyl carbonate (DMC), diphenyl carbonate (DPC), and bisphenol A polycarbonate (BPA-PC) is a reality, finding its driving force from the industrialization of alternative routes by EniChem (Italy) and UBE (Japan). This favorable situation can be foreseen for…

CO2: from waste to resource for methanol-based processes

2009

This paper reports on research aiming at developing sustainable processes for the production of methanol (CH3OH) and dimethyl carbonate (DMC, (CH3)2CO3) using carbon dioxide (CO2) as a raw material. Using carbon dioxide as a raw material has several advantages; it is non-toxic, in abundant supply, and promises innovative routes to the production of commodity chemicals. Methanol and dimethyl carbonate are important products and feedstocks of the chemical industry. Methanol is produced commercially from synthesis gas, but it is also possible to use carbon dioxide as a feedstock. Conventional production of dimethyl carbonate involves the use of toxic phosgene or carbon monoxide, while the met…

Insertion reaction of carbon dioxide into Sn-OR bond. Synthesis, structure and DFT calculations of di- and tetranuclear isopropylcarbonato tin(IV) co…

2006

The reaction of carbon dioxide with the stannane nBu2Sn(OiPr)2 and distannoxane [nBu2(iPrO)Sn]2O leads to the selective insertion into one Sn-OiPr bond generating the corresponding nBu2Sn(OiPr)(OCO2(i)Pr) and nBu2(iPrO)SnOSn(OCO2(i)Pr)nBu2 species. Both compounds are characterised by multinuclear NMR, FT-IR and single-crystal X-ray crystallography. In the solid state, they adopt a dimeric arrangement with bridging isopropoxy and terminal isopropylcarbonato ligands. The X-ray crystal structure of the dinuclear stannane shows that the Sn2O2 ring and the two Sn-OCO2C fragments are nearby coplanar. The same holds for the ladder-type tetranuclear distannoxane. The dimeric structures are also evi…

The role of distannoxanes in the synthesis of dimethyl carbonate from carbon dioxide

2003

Abstract The synthesis, characterization, and reactivity of 1,3-dimethoxytetrabutyldistannoxane were investigated in connection to the mechanism of the selective synthesis of dimethyl carbonate from CO2 and methanol. A new distannoxane, 1-methoxy-3-methylcarbonatotetrabutyldistannoxane, resulting from a 1:1 adduct with CO2 was isolated and characterised by volumetry, multinuclear NMR and IR spectroscopies. When this compound was submitted to 20 MPa of CO2 at 423 K in toluene no dimethyl carbonate was formed, conversely to dibutyldimethoxystannane. However, when methanol was the solvent, dimethyl carbonate was selectively produced. A promoting effect of Si(OCH3)4 was evidenced through methox…

Di-n-butyltin oxide as a chemical carbon dioxide capturer

2010

Abstract Several synthetic routes to the decakis(di-n-butyltin(IV)) oxocluster, (n-Bu2SnO)6[(n-Bu2SnOCH3)2(CO3)]2 (1), a diorganotin compound previously shown to belong to the class of organotins able to store carbon dioxide, as well as its reactivity toward dimethyl carbonate (DMC), are described. The synthetic route from n-Bu2SnO and DMC was applied for the preparation of the ethoxy analogue of 1, oxocluster 2, using diethyl carbonate. The structural relationship connecting cluster 1, with its precursor PRE-1 isolated from recycling experiments and n-Bu2SnO is discussed. For this purpose, the reactivity of PRE-1 with trifluoromethanesulfonic acid was investigated in order to trace structu…

Direct synthesis of dimethyl carbonate with supercritical carbon dioxide: characterization of a key organotin oxide intermediate

2006

The direct synthesis of dimethyl carbonate (DMC) using carbon dioxide as solvent and reagent for its fixation to methanol was explored with din-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…

From CO2 to dimethyl carbonate with dialkyldimethoxystannanes: the key role of monomeric species.

2011

International audience; The formation of dimethyl carbonate (DMC) from CO(2) and methanol with the dimer [n-Bu(2)Sn(OCH(3))(2)](2) was investigated by experimental kinetics in support of DFT calculations. Under the reaction conditions (357-423 K, 10-20 MPa), identical initial rates are observed with three different reacting mixtures, CO(2)/toluene, supercritical CO(2), and CO(2)/methanol, and are consistent with the formation of monomeric di-n-butyltin(iv) species. An intramolecular mechanism is, therefore, proposed with an Arrhenius activation energy amounting to 104 ± 10 kJ mol(-1) for DMC synthesis. DFT calculations on the [(CH(3))(2)Sn(OCH(3))(2)](2)/CO(2) system show that the exothermi…

Catena-poly[[di-n-butyltin(IV)]-mu-trifluoromethanesulfonato-[[di-n-butyl(trifluoromethanesulfonato)tin(IV)]-di-mu-hydroxo]]

2006

International audience

A novel two-dimensional organostannoxane coordination network promoted by phenazine: Synthesis, characterization and X-ray structure of

2009

Abstract Reaction of the dimeric hydroxo di-n-butylstannane trifluoromethanesulfonato complex [n-Bu2Sn(μ-OH)(H2O)0.5(η1-O3SCF3)]2 (1) with phenazine (C12H8N2, Phz) (2) in dichloromethane at room temperature in a 1:3 molar ratio yielded the novel two-dimensional organometallic coordination polymer 2 ∞ { [ n - Bu 2 ( μ -OH ) SnOSn ( μ - η 2 - O 3 SCF 3 ) n - Bu 2 ] 2 [ n - Bu 2 ( μ -OH ) SnOSn ( η 1 - O 3 SCF 3 ) n - Bu 2 ] 2 } (3), together with the phenazinium trifluoromethanesulfonate salt [C12H9N2]+ [CF3SO3]−, crystallographically isolated in two different structural arrangements, free 4 and in π–π aromatic stacking interaction with independent intercalated non-protonated phenazine molecu…

Carbon dioxide conversion to dimethyl carbonate: The effect of silica as support for SnO2 and ZrO2 catalysts

2011

International audience; Abundant in nature, CO2 poses few health hazards and consequently is a promising alternative to phosgene feedstock according with the principles of Green Chemistry and Engineering. The synthesis organic carbonates from CO2 instead of phosgene is highly challenging as CO2 is much less reactive. As part of our ongoing research on the investigation of catalysts for dimethyl carbonate (DMC) synthesis from methanol and CO2, we herein report results aimed at comparing the catalytic behavior of new SnO2-based catalysts with that of ZrO2. Silica-supported SnO2 and ZrO2 exhibit turnover numbers which are an order of magnitude higher than those of the unsupported oxides. Tin-b…

Can Green Dimethyl Carbonate Synthesis be More Effective? A Catalyst Recycling Study Benefiting from Experimental Kinetics and DFT Modeling

2014

Dibutyldimethoxystannanes are known to catalyze the reaction between carbon dioxide and methanol leading to dimethyl carbonate. Despite similarities between din-butyl- and ditert-butyldimethoxystannane, the recycled complexes have different structural features. In the din-butyl series, a decatin(IV) complex has been characterized and is less active than the stannane precursor. Kinetic experiments likely indicate that all the tin centers are not active, which is confirmed in comparing with the related dinuclear 1,3-dimethoxytetran-butyldistannoxane complex. In the ditert-butyl series, the tritin(IV) complex isolated upon recycling features the steric effect of bulky tBu ancillary ligands. In…

Tin-based mesoporous silica for the conversion of CO2 into dimethyl carbonate.

2011

Sn-based SBA-15 was prepared by reacting di-n-butyldimethoxystannane with SBA-15 pretreated with trimethylchlorosilane (TMCS) to cap the external hydroxyl groups. Small-angle X-ray diffraction (SXRD), infrared spectroscopy (IR), nitrogen adsorption/desorption, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission (ICP-AES) measurements allow us to propose that the organotin species are located within the pore channels of the mesoporous host. This novel material catalyzes selectively the coupling of CO(2) with methanol to dimethyl carbonate (DMC). The reaction time-conversion dependence shows that a turnover number (TON) of 1…

Reduction and catalytic behaviour of heterobimetallic copper–lanthanide oxides

2008

Abstract The reduction of the heterobimetallic copper–lanthanide oxides 2CuO·CeO2 and 3CuO·Ln2CuO4 (Ln = La, Pr, Nd) was studied by H2-TG/DTA and H2-TPR. All systems exhibit two main reduction steps accompanied by mass losses in the temperature range 20–1000 °C. The first step was attributed to CuO reduction, whereas the second step is due either to copper reduction in the Ln2CuO4 phase with the concomitant formation of Ln2O3 or to the surface reduction of CeO2. The products were characterized by XRD, SEM, EDX, and BET techniques and are better described as supported copper type materials. They were active for the mesityl oxide (4-methyl-2-penten-2-one) gas phase hydrogenation.

A comparative study of methanol carbonation on unsupported SnO2 and ZrO2

2009

International audience; The aim of this work was to explore the catalytic properties of SnO2 in the coupling of methanol with carbon dioxide to afford dimethyl carbonate. SnO2 nanopowders were produced by hydrolysis of tin tetra-tert-butoxide dissolved in n-butanol. The samples were much more active than a commercial one due to their higher surface areas. In addition, they exhibited excellent recyclability. However, comparison with ZrO2, prepared and tested under the same experimental conditions, showed that zirconia-based catalysts were more selective and are, among the heterogeneous catalysts already reported, still the more selective. SnO2 also catalyzed the formation of dimethyl ether l…

Reactivity of dialkoxydibutylstannanes toward carbon dioxide: A DFT study of electronic and steric effects

2012

Abstract DFT calculations were performed for the reaction of CO 2 with the monomeric species, R′ 2 Sn(OR) 2 , (R = R′ = CH 3 ; R = CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , R′ =  n -Bu) for assessing the role of electronic and steric effects in the kinetics and thermodynamics of CO 2 insertion into Sn–OR bonds. The reaction pathways are exothermic and involve the successive insertion into the two Sn–OR bonds. The driving force for insertion is ascribed to a charge-transfer between the HOMO of the complexes, mainly localized on the oxygen atom of the alkoxy ligands, and the LUMO of CO 2 . Interestingly enough, the energy barrier of the second insertion is much lower by around 27 kJ mol −1 , and quite…

The ionic tin(IV) complex tri-μ2-methoxy-μ3-oxo-tris[di-tert-butyltin(IV)] tri-μ2-methoxy-bis[tert-butyldimethoxystannate(IV)]

2004

The solid-state of the title compound, [Sn3(C4H9)6(CH3O)3O][Sn2(C4H9)2(CH3O)7], consists of distinct [tBu6Sn3(μ-OCH3)3(μ3-O)]+ cations and [tBu2Sn2(OCH3)4(μ-OCH3)3]− anions, apparently formed as a result of slow hydro­lysis of pure di(tert-butyl)­di­methoxy­stannane, tBu2Sn(OCH3)2. In the monocation, the coordin­ation about the Sn atoms is distorted trigonal bipyramidal, and, in the monoanion, distorted octahedral. The trigonal bipyramidal arrangement induces planarity of the Sn3O4 motif.

Ongelmasta hyödyke: hiilidioksidi metanolin ja dimetyylikarbonaatin raakaaineena

2006

International audience