Carbon Dioxide Fixation by the Cooperative Effect of Organotin and Organotellurium Oxides

Abstract

Hypervalenz und Bildung sekundärer Bindungen sind die treibenden Kräfte hinter der raschen Absorption von gasförmigem Kohlendioxid durch zwei Organotellur‐ und Organozinnoxide und der unerwarteten Bildung eines Tellurastannoxanclusters (siehe Struktur; dunkelrot Te, schwarz Sn, grau C, hellrot O). Die Absorption ist reversibel: Bei Temperaturen zwischen 90 und 145 °C wird Kohlendioxid freigesetzt.

Carbon Dioxide Activation Assisted by a Bis(chlorodimethylsilyl)cyclopentadienyl Titanium Compound

“…This type of reaction is common for the late‐transition metals3 and is known for main‐group organometallic species 4. Nevertheless, the carbonato derivatives reported for complexes of Group 4–6 metals are synthesized by alternative methods5 based on reactions of metal precursor compounds with carbonate salts X 2 CO 3 (X=K, Bu 4 N) and NH 4 HCO 3 or by methods that involve the disproportionation of CO 2 .…”

Carbon Dioxide Activation Assisted by a Bis(chlorodimethylsilyl)cyclopentadienyl Titanium Compound

“…This type of reaction is common for the late‐transition metals3 and is known for main‐group organometallic species 4. Nevertheless, the carbonato derivatives reported for complexes of Group 4–6 metals are synthesized by alternative methods5 based on reactions of metal precursor compounds with carbonate salts X 2 CO 3 (X=K, Bu 4 N) and NH 4 HCO 3 or by methods that involve the disproportionation of CO 2 .…”

First Example of a Hydrated Monoorganotin Cation: Synthesis and Structure of [{PhSn(H2O)3(μ-OH)}2][{1,5-C10H6-(SO3)2}2]

“…Recently there has been interest in the use of Sn−C bond cleavage reactions among aryl- and alkyltin compounds as viable synthetic procedures for preparing organooxotin compounds . Although most of these reactions occur with carboxylic/phosphonic/phosphinic acids, recent reports from our laboratory and that of Beckmann suggested that Sn−C bond cleavage reactions can also occur in the reactions of organotin precursors with sulfonic acids. Spurred by this, we investigated the reaction of Ph 2 SnO with naphthalene-1,5-disulfonic acid tetrahydrate.…”

12‐Membered Macrocycles Containing Ditelluroxane and Selenotelluroxane Units

“…Beckmann and coworkers have performed pioneering work in this field by carrying out reactions of diorganotellurium oxides with various protic ligands, such as carboxylates,3 phosphinates,4 sulfonates,4 and diorganosilane diols,5 which resulted in the formation of products that show rich structural variation. Beckmann and coworkers have also shown that solutions of di‐ p ‐anisyltellurium oxide and di‐ tert ‐butyltin oxide can absorb gaseous CO 2 rapidly, which resulted in the formation of tellurastannoxanes that evolved the absorbed CO 2 at low temperatures 6. Chandrasekhar and coworkers have investigated the reaction of a cyclic phosphinic acid with diorganotellurium dihalide, which led to the assembly of an unprecedented 12‐membered macrocycle, which is capped by halogen atoms on both sides;7 the authors suggest that these macrocycles can be considered as analogues of “inverse crowns”8 and “ anti ‐crowns” 9.…”

Carbon Dioxide Activation Assisted by a Bis(chlorodimethylsilyl)cyclopentadienyl Titanium Compound

“…This type of reaction is common for the late‐transition metals3 and is known for main‐group organometallic species 4. Nevertheless, the carbonato derivatives reported for complexes of Group 4–6 metals are synthesized by alternative methods5 based on reactions of metal precursor compounds with carbonate salts X 2 CO 3 (X=K, Bu 4 N) and NH 4 HCO 3 or by methods that involve the disproportionation of CO 2 .…”

First Example of a Hydrated Monoorganotin Cation: Synthesis and Structure of [{PhSn(H2O)3(μ-OH)}2][{1,5-C10H6-(SO3)2}2]

“…Recently there has been interest in the use of Sn−C bond cleavage reactions among aryl- and alkyltin compounds as viable synthetic procedures for preparing organooxotin compounds . Although most of these reactions occur with carboxylic/phosphonic/phosphinic acids, recent reports from our laboratory and that of Beckmann suggested that Sn−C bond cleavage reactions can also occur in the reactions of organotin precursors with sulfonic acids. Spurred by this, we investigated the reaction of Ph 2 SnO with naphthalene-1,5-disulfonic acid tetrahydrate.…”

12‐Membered Macrocycles Containing Ditelluroxane and Selenotelluroxane Units

“…Beckmann and coworkers have performed pioneering work in this field by carrying out reactions of diorganotellurium oxides with various protic ligands, such as carboxylates,3 phosphinates,4 sulfonates,4 and diorganosilane diols,5 which resulted in the formation of products that show rich structural variation. Beckmann and coworkers have also shown that solutions of di‐ p ‐anisyltellurium oxide and di‐ tert ‐butyltin oxide can absorb gaseous CO 2 rapidly, which resulted in the formation of tellurastannoxanes that evolved the absorbed CO 2 at low temperatures 6. Chandrasekhar and coworkers have investigated the reaction of a cyclic phosphinic acid with diorganotellurium dihalide, which led to the assembly of an unprecedented 12‐membered macrocycle, which is capped by halogen atoms on both sides;7 the authors suggest that these macrocycles can be considered as analogues of “inverse crowns”8 and “ anti ‐crowns” 9.…”

Carbon Dioxide Activation Assisted by a Bis(chlorodimethylsilyl)cyclopentadienyl Titanium Compound

“…This type of reaction is common for the late‐transition metals3 and is known for main‐group organometallic species 4. Nevertheless, the carbonato derivatives reported for complexes of Group 4–6 metals are synthesized by alternative methods5 based on reactions of metal precursor compounds with carbonate salts X 2 CO 3 (X=K, Bu 4 N) and NH 4 HCO 3 or by methods that involve the disproportionation of CO 2 .…”

First Example of a Hydrated Monoorganotin Cation: Synthesis and Structure of [{PhSn(H2O)3(μ-OH)}2][{1,5-C10H6-(SO3)2}2]

“…Recently there has been interest in the use of Sn−C bond cleavage reactions among aryl- and alkyltin compounds as viable synthetic procedures for preparing organooxotin compounds . Although most of these reactions occur with carboxylic/phosphonic/phosphinic acids, recent reports from our laboratory and that of Beckmann suggested that Sn−C bond cleavage reactions can also occur in the reactions of organotin precursors with sulfonic acids. Spurred by this, we investigated the reaction of Ph 2 SnO with naphthalene-1,5-disulfonic acid tetrahydrate.…”

12‐Membered Macrocycles Containing Ditelluroxane and Selenotelluroxane Units

“…Beckmann and coworkers have performed pioneering work in this field by carrying out reactions of diorganotellurium oxides with various protic ligands, such as carboxylates,3 phosphinates,4 sulfonates,4 and diorganosilane diols,5 which resulted in the formation of products that show rich structural variation. Beckmann and coworkers have also shown that solutions of di‐ p ‐anisyltellurium oxide and di‐ tert ‐butyltin oxide can absorb gaseous CO 2 rapidly, which resulted in the formation of tellurastannoxanes that evolved the absorbed CO 2 at low temperatures 6. Chandrasekhar and coworkers have investigated the reaction of a cyclic phosphinic acid with diorganotellurium dihalide, which led to the assembly of an unprecedented 12‐membered macrocycle, which is capped by halogen atoms on both sides;7 the authors suggest that these macrocycles can be considered as analogues of “inverse crowns”8 and “ anti ‐crowns” 9.…”