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

Beckmann, Jens; Dakternieks, Dainis; Duthie, Andrew; Lewcenko, Naomi A.; Mitchell, Cassandra

doi:10.1002/ange.200460155

Cited by 8 publications

(4 citation statements)

References 25 publications

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“…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.…”

Section: Introductionmentioning

confidence: 99%

12‐Membered Macrocycles Containing Ditelluroxane and Selenotelluroxane Units

Srungavruksham

Baskar

2011

Eur J Inorg Chem

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The reaction of benzeneseleninic acid with bis(p‐methoxyphenyl)tellurium dihalide [halide = Cl (1), Br (2)] afforded colorless crystals in moderate yield. Single‐crystal X‐ray diffraction revealed the formation of 12‐membered macrocycles [(p‐MeO‐C6H4)2Te(μ‐O)(μ‐PhSeO2)(μ4‐X)]2 [X = Cl (1), Br (2)] where the halogen atoms, which are stabilized by Te–X interactions, cap the macrocycle on both sides. The reaction of NaI with 1 afforded the iodo‐capped macrocycle [(p‐MeO‐C6H4)2Te(μ‐O)(μ‐PhSeO2)(μ4‐I)]2 (3) in good yield. In the solid‐state structures of 1–3, the alignment of the phenyl group on Se changes with respect to the macrocycle. Macrocycle 3 shows rare Se–π interactions, which lead to the formation of a supramolecular polymeric network. Further reaction of methaneseleninic acid with bis(p‐methoxyphenyl)tellurium dichloride in methanol in the presence of triethylamine afforded a 12‐membered macrocycle [(p‐MeO‐C6H4)2Te(μ‐O)(μ‐MeSeO2)(μ4‐Cl)]2 (4), which is structurally similar to 1–3.

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Section: Introductionmentioning

confidence: 99%

12‐Membered Macrocycles Containing Ditelluroxane and Selenotelluroxane Units

Srungavruksham

Baskar

2011

Eur J Inorg Chem

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“…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 .…”

Section: Methodsmentioning

confidence: 99%

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

et al. 2005

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A great deal of interest has focused on the role of metal ions as the active centers in the fixation of CO 2 and its transformation.[1] Activation of CO 2 by hydroxo and oxo metal complexes to afford metal hydrogencarbonato and carbonato species, respectively, is related to the function of the carbonic anhydrase metalloenzyme, [2] which catalyzes the physiologically important hydration of CO 2 to hydrogencarbonate [Eq. (1)].This type of reaction is common for the late-transition metals [3] 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 methods [5] 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 .Herein, we describe the use of the bis(chlorodimethylsilyl)cyclopentadienyl titanium(iv) compound 1, [6] which was reported previously for the in situ activation of CO 2 . The carbonato titanium(iii) derivative 3 was serendipitously obtained when a dilute solution of 1 in wet toluene was exposed to air for several days (Scheme 1). This reaction proceeded in better yield (43 % after purification) when a solution of 1 in toluene was treated with a saturated aqueous solution of CO 2 to give 3, which was isolated as an analytically pure and highly air-stable diamagnetic orange crystalline solid. However, hydrolysis of 1 carried out in the presence of NEt 3 resulted in no reaction with CO 2 and the m-oxo titanium(iv) derivative 2 and NEt 3 ·HCl being obtained (Scheme 1). The reaction of 1 with K 2 CO 3 in THF or toluene afforded a mixture of unidentified compounds that did not contain 3.Hydrolysis of the Group 4 metal/chloro complexes usually proceeds with initial transformation of the metal-chlorine bonds so that intermediate complexes are formed which contain rather uncommon, discrete terminal Group 4 metalhydroxo bonds.[7] These species subsequently condense to give polynuclear compounds stabilized by m-oxo bridges.[8] We propose that the carbonato complex 3 results from the in situ formation of intermediate SiÀOH/TiÀOH terminal bonds (see A and B in Scheme 1) and a further insertion reaction of CO 2 with simultaneous reduction to the highly stable titanium(iii) compound 3. This mechanism of formation is consistent with the high stability of 3, which remains unaltered when left for weeks in air; with the formation of the m-oxo complex 2 in the presence of a deprotonating agent; and also with the observed stability of 2, as it did not react with CO 2 to give 3 after several days at temperatures higher than 120 8C.The 1 H NMR spectrum (CDCl 3 , 258C) of complex 3 shows behavior expected for a C 2h -symmetric molecule with an A 2 B spin system for the cyclopentadiene (Cp) protons and with two resonances of the two nonequivalent methyl groups of the four equivalent {SiMe 2 } fragments (see Experimental Section). The resonances of the carbon atoms of the two equivalent bridging carbonato ...

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“…B. [{( p ‐MeOC 6 H 4 ) 2 TeOSn( t Bu 2 )CO 3 } 2 ] 3, [{(p‐Me 2 NC 6 H 4 ) 2 TeOSn( t Bu 2 )(CO) 3 } 2 ] 4 und [( p ‐MeOC 6 H 4 ) 2 Te(OSn t Bu 2 OH) 2 ] 2 5.…”

Section: Introductionunclassified

Synthese und Eigenschaften von Ph₃Sn‐substituierten Telluraten – Die Kristallstrukturen von trans‐[(Ph₃SnO)₄Te(OH)₂] und trans‐[(Ph₃SnO)₂Te(OMe)₄]

Herntrich

Merzweiler

2010

Zeitschrift anorg allge chemie

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The reaction of Te(OH)6 with Ph3SnOH in ethanol leads to the formation of trans‐[(Ph3SnO)4Te(OH)2] (1). Compound 1 crystallizes triclinic in the space group P\bar{1} with a = 996.6(2) pm, b = 1365.4(3) pm, c = 1368.2(3) pm and α = 71.15(2)°, β = 71.48(2)°, γ = 74.81(3)° (at 220 K). The molecular structure of 1 consists of a tellurium atom, which is coordinated nearly octahedrally by four Ph3SnO units and two hydroxyl groups that are trans to each other. The Te–O bond lengths are in the range of 190.5(2) and 193.7(2) pm. Treatment of 1 with methanol under reflux yields trans‐[(Ph3SnO)2Te(OMe)4] (2). Compound 2 crystallizes triclinic in the space group P\bar{1} with a = 1012.8(1) pm, b = 1422.4(2) pm, c = 1618.1(2) pm, and α = 100.44(1)°, β = 107.92(1)°, γ = 110.66(1)° (at 220 K). 2 forms centrosymmetric molecules in which the tellurium atom is surrounded nearly octahedrally by four methoxy groups and two trans arranged Ph3SnO units. The Te–O bond lengths of 187.9(3)–194.5(3) pm are similar to those observed in 1.

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

Cited by 8 publications

References 25 publications

12‐Membered Macrocycles Containing Ditelluroxane and Selenotelluroxane Units

12‐Membered Macrocycles Containing Ditelluroxane and Selenotelluroxane Units

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

Synthese und Eigenschaften von Ph₃Sn‐substituierten Telluraten – Die Kristallstrukturen von trans‐[(Ph₃SnO)₄Te(OH)₂] und trans‐[(Ph₃SnO)₂Te(OMe)₄]

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

Cited by 8 publications

References 25 publications

12‐Membered Macrocycles Containing Ditelluroxane and Selenotelluroxane Units

12‐Membered Macrocycles Containing Ditelluroxane and Selenotelluroxane Units

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

Synthese und Eigenschaften von Ph3Sn‐substituierten Telluraten – Die Kristallstrukturen von trans‐[(Ph3SnO)4Te(OH)2] und trans‐[(Ph3SnO)2Te(OMe)4]

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Synthese und Eigenschaften von Ph₃Sn‐substituierten Telluraten – Die Kristallstrukturen von trans‐[(Ph₃SnO)₄Te(OH)₂] und trans‐[(Ph₃SnO)₂Te(OMe)₄]