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

Ballivet‐Tkatchenko, Danielle; Jerphagnon, Thomas; Ligabue, Rosane Angélica; Plasseraud, Laurent; Poinsot, Didier

doi:10.1016/s0926-860x(03)00647-1

Cited by 72 publications

(46 citation statements)

References 28 publications

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“…It has been shown that the double CO 2 insertion on the monomer to afford Bu 2 Sn[OC(O)OCH 3 ] 2 is thermodynamically possible [30,31,33], but the compounds were not isolated nor their presence ascertained in the catalytic runs. Thermal treatment transforms A into B with the concomitant formation of DMC.…”

Section: Tin-based Catalystsmentioning

confidence: 99%

Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates

et al. 2014

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Dialkylcarbonates, (RO)2CO, can be prepared from alcohols and CO2. Such reaction is clean (water is the co-product) but thermodynamically disfavored. In principle, the reaction mechanism of formation of carbonates requires the acid-base activation of alcohols. Existing data support that the first step is the formation of the alkoxo group RO^- that reacts with CO2 to give the hemicarbonate moiety ROC(O)O^-. The latter converts into the relevant carbonate (RO)2CO following different pathways depending on the catalyst used. DFT calculations have been used in a few cases to support the reaction mechanism. Transition states relevant to various mechanistic scenarios have been identified. The results indicated that the relative energies of these transition states depend on the nature of the alkyl group and the molecularity of the reactive step. Organic catalysts, homogeneous-, heterogenized- and heterogeneous-metal systems are discussed in this paper and the known relevant mechanisms compared. Water represents a serious limitation to equilibrium shift to the right and can affect the catalysts. Techniques used to remove water are also discussed

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Section: Tin-based Catalystsmentioning

confidence: 99%

Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates

et al. 2014

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“…These materials could also act as catalysts for organic synthesis such as production of polyurethane foams and electrocoat (E-coat) coatings. In addition, it was shown that organotin compounds such as distannanes could catalyze the reaction of direct synthesis of dimethyl carbonate (DMC) from CO 2 and methanol [2][3][4][5]. This process gains much interest because of its environmentally benign character and the versatility of DMC as an attractive eco-friendly alternative to both methyl halides (or dimethyl sulfate) and phosgene in methylation and carbonylation processes, respectively [6], and as a fuel additive [2][3][4][5].…”

Section: Introductionmentioning

confidence: 99%

In Situ Preparation of Functional Heterogeneous Organotin Catalyst Tethered on SBA-15

Fan

Zhang

et al. 2007

Catal Lett

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A stable heterogeneous organotin catalyst has been prepared by in situ tethering organotin compounds on SBA-15. This was verified by XRD, TEM, N 2 adsorption/ desorption at -196°C, FTIR and diffuse reflectance UVvis spectral techniques. This material was much more active than the sample prepared by the grafting method for the direct synthesis of dimethyl carbonate (DMC) from methanol and CO 2 despite that its catalytic activity was dependent on the organotin amount. This could be attributed to the formation of organotin clusters with different structures and the larger surface area. After immobilization on the SBA-15 mesoporous material, the six-coordinated organotin clusters showed higher activity, compared to the tetrahedral Sn species. With increasing reaction temperature and CO 2 pressure, the catalytic activity considerably increased.

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“…In the past, similar architectures, then described as a bicapped tetrahedron or a "chain" of three tetrahedra sharing faces, were observed in particular for hexanuclear clusters of lead and osmium (β -[Pb 6 O(OH) 6 4+ ] [30], Os 6 (CO) 18 [31]). To the best of our knowledge, compound 3 constitutes the first example for organotin(IV) complexes presenting such a structure.…”

Section: Molecular Structure Of [(C 7 H 7 Sn) 6 (µ 4 -O)(µ-oh) 11 -(Hmentioning

confidence: 97%

“…Formerly, investigating the direct synthesis of organic carbonates from carbon dioxide and alcohols promoted by organometallic tin(IV) precursors [18], and during recycling experiments, we isolated a deca(organotin(IV)) oxo cluster, characterized as (nBu 2 SnO) 6 [(n-Bu 2 SnOCH 3 ) 2 (CO 3 )] 2 and arranged in a pair of coplanar [(n-Bu 2 Sn) 5 O] 5 ladders bridged by two carbonate groups ( Fig. 1) [19].…”

Section: Introductionmentioning

confidence: 99%

Unprecedented Hexa- and Undecanuclear Frameworks of Two New Tin(IV) Oxo Clusters Resulting from Partial Debenzylation Reactions

Plasseraud

Cattey

Richard

2010

Zeitschrift Für Naturforschung B

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A new and facile synthetic route to the known neutral cluster ((PhCH 2 ) 2 SnO) 6 [((PhCH 2 ) 2 SnOH) 2 -(CO 3 )] 2 (2) as well as its reactivity toward trifluoromethanesulfonic acid (HO 3 SCF 3 , TfOH) are reported. The solid-state structure of the new solvate 2·6C 7 H 8 has been determined by single-crystal X-ray diffraction. The core of 2 can be described as a pair of coplanar pentanuclear [(PhCH 2 ) 2 SnO] 5 ladders bridged at their ends by two carbonate groups. Successive additions of TfOH to a suspension of 2 in CD 3 CN were monitored by 119 Sn{ 1 H} NMR spectroscopy showing the transformation of the fingerprint of 2 (δ = −244, −246, −306 ppm), via new upfield signals, to a final broad resonance located at δ = −474 ppm. Thereafter, two unprecedented ionic monobenzyltin(IV) oxo clusters, 3 and 4, resulting from a debenzylation reaction and exhibiting unusual hexa-and undecanuclear frameworks, respectively, have been isolated as single crystals. IntroductionOrganotin compounds with Sn-O bonds have a diversity of solid-state structures, from discrete mononuclear compounds to complex clusters and multidimensional networks. Pioneering work in the field of organotin-oxo clusters is attributable to Holmes and Chandrasekhar who in the 1980's discovered several unexpected polynuclear structures and published the first reviews relating to the classification of these compounds [1]. Since then, the inventory of structures has regularly been updated; it reveals a profuse structural diversity [2]. Indeed, on the basis of X-ray crystallographic studies, a great variety of shapes has already been identified for organotin-oxo derivatives which include prismane [3], butterfly [4], ladder [5], O-and Scapped cluster [6], drum [7], cube [8], double cube [9], football cage [10], crown [11], extended cage [12], and coordination polymer types [13]. Moreover, the structural interrelationship between these polynuclear arrangements has been clearly established, highlighting possible mechanisms of interconversion from one form to another [14]. In the past decade, with the growing interest in the assembly of the metal-organic frameworks 0932-0776 / 10 / 1100-1293 $ 06.00 c 2010 Verlag der Zeitschrift für Naturforschung, Tübingen · http://znaturforsch.com (MOFs), organotin-oxo moieties have also been used as building blocks for designing supramolecular architectures with remarkably large cavities [15]. From a synthetic point of view, organotin assemblies containing Sn-O bonds are generally obtained from the reaction of organotin precursors (such as organotin oxides and hydroxides) in the presence of phosphonic, phosphinic, carboxylic, and sulfonic acids at room temperature or under reflux conditions. Recently, reactions with arylarsonic acids were also explored [16]. In numerous examples, the cleavage of Sn-C bonds leads to the formation of Sn-O bonds [17].Formerly, investigating the direct synthesis of organic carbonates from carbon dioxide and alcohols promoted by organometallic tin(IV) precursors [18], and during recycling experime...

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

Cited by 72 publications

References 28 publications

Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates

Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates

In Situ Preparation of Functional Heterogeneous Organotin Catalyst Tethered on SBA-15

Unprecedented Hexa- and Undecanuclear Frameworks of Two New Tin(IV) Oxo Clusters Resulting from Partial Debenzylation Reactions

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