Distortion of “tetrahedral” C3v coordination in the R3CO moiety due to the reduction of molecular symmetry: X-ray,. conformational, and quantum-chemical study

Slovokhotov, Yu.L.; Timofeeva, T. V.; Antipin, M. Yu.; Struchkov, Yu. T.

doi:10.1016/0022-2860(84)80250-1

Cited by 40 publications

(12 citation statements)

References 19 publications

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“…The H-O-O-C torsion angle is 99.78 and is similar to that of hydrogen peroxide [9] or the uncoordinated tert-butyl hydrogen peroxide. [10] Compound 5 forms one-dimensional coordination polymers in the solid state by hydrogen bonding between the protons of HOOCMe 3 molecules and negatively charged oxygen atoms of the bridging ligands (O2ÀO4' 253.1 pm; O4' by x+1, y, z). The completely deprotonated compound (LiOOCMe 3 ) was reported before and has a dodecameric structure.…”

Section: (O)]mentioning

confidence: 99%

See 1 more Smart Citation

Reducing GaH and GaC Bonds in Close Proximity to Oxidizing Peroxo Groups: Conflicting Properties in Single Molecules

Uhl

Halvagar

Claesener

2009

Chemistry A European J

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Treatment of [Li(H(2)Ga{CH(SiMe(3))(2)}(2))]2 OEt(2) (12 OEt(2)) with two equivalents of tert-butyl hydrogen peroxide, H-O-O-CMe(3), afforded the organogallium peroxide [({(Me(3)Si)(2)HC}(2)Ga(OH)(OOCMe(3))Li)(2)] (3), which possesses oxidizing peroxo groups in close proximity to reducing Ga-C bonds. The lithium atoms of the dimeric formula units are coordinated by both oxygen atoms of the peroxides and by two hydroxo groups. The cleavage of the Ga--C bond was not observed, even when an excess of H-O-O-CMe(3) was applied. Instead, the adduct [{(Me(3)Si)(2)HC}(2)Ga(OH)(OOCMe(3))(2)Li(2)(HOOCMe(3))] (4) was isolated, which has an intact H-O-O-CMe(3) molecule terminally attached to lithium. A similar structural motif was found for the compound [(LiOOCMe(3))(2)(HOOCMe(3))(2)] (5). The trihydrido gallanate [Li(H(3)Ga-{CH(SiMe(3))(2)})]OEt(2) (2) yielded the unique peroxide [({(Me(3)Si)(2)HC}--Ga(H)(OOCMe(3))(2)Li)(2)] (6) under similar conditions that possesses Ga-C and even more reactive Ga-H bonds beside peroxo groups. It decomposed at room temperature by the insertion of oxygen atoms into the Ga-H bonds and the formation of [({(Me(3)Si)(2)HC}-Ga(OH)(OCMe(3))(OOCMe(3))Li)(2)] (7), which was isolated in a low yield. Further decomposition gave the complete degradation of all peroxo groups with the formation of a relatively complicated Li(4)Ga(4)O(8) cage (8).

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Section: (O)]mentioning

confidence: 99%

“…The OÀO bond length (149.2 pm) corresponds to standard values. [2,5,6,[9][10][11] Another compound (4) was formed as the main component when 1·2 OEt 2 was treated with a larger excess (7 equivalents) of tert-butyl hydrogen peroxide [Eq. (3)].…”

Section: (O)]mentioning

confidence: 99%

Reducing GaH and GaC Bonds in Close Proximity to Oxidizing Peroxo Groups: Conflicting Properties in Single Molecules

Uhl

Halvagar

Claesener

2009

Chemistry A European J

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“…At this point a Rietveld refinement in the Cmcm space group was performed, with the MTBE guest molecule treated as a rigid body. Its conformation was taken from Slovokhotov et al [31]. These rigid body constrains were progressively reduced and, as a result, the C2 carbon once again shifted up to the position found in the previous refinements.…”

Section: Zeoliteorganicmentioning

confidence: 99%

Location of MTBE and toluene in the channel system of the zeolite mordenite: Adsorption and host–guest interactions

Arletti

Martucci

Alberti

et al. 2012

Journal of Solid State Chemistry

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a b s t r a c tThis paper reports a study of the location of Methyl Tertiary Butyl Ether (MTBE) and toluene molecules adsorbed in the pores of the organophylic zeolite mordenite from an aqueous solution. The presence of these organic molecules in the zeolite channels was revealed by structure refinement performed by the Rietveld method. About 3 molecules of MTBE and 3.6 molecules of toluene per unit cell were incorporated into the cavities of mordenite, representing 75% and 80% of the total absorption capacity of this zeolite. In both cases a water molecule was localized inside the side pocket of mordenite. The saturation capacity determined by the adsorption isotherms, obtained by batch experiments, and the weight loss given by thermogravimetric (TG) analyses were in very good agreement with these values. The interatomic distances obtained after the structural refinements suggest MTBE could be connected to the framework through a water molecule, while toluene could be bonded to framework oxygen atoms. The rapid and high adsorption of these hydrocarbons into the organophylic mordenite zeolite makes this cheap and environmental friendly material a suitable candidate for the removal of these pollutants from water.

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“…This geometry may be explained on the basis of a maximum of σ C1−C2 → σ * O−O hyperconjugation 50 . The observed narrow range for the O−C1−C2 angles obviously poses an appropriate balance between the stabilization gained by the orbital interaction and the angle strain caused by the bend 9 .…”

Section: Tetrahedral Distortionmentioning

confidence: 99%

“…phthalimidoperoxyalkanoic acids, was extensively studied with the aim to find compounds of high solid state stability to serve as potential low-temperature laundry bleaches. In 1,3-dihydro-1,3-dioxo-2H -isoindole-2-peroxyhexanoic acid (50) …”

Section: Alkanoyl Peracidsmentioning

confidence: 99%

The Structural Chemistry of Acyclic Organic Peroxides

Hartung

Svoboda

2009

Patai's Chemistry of Functional Groups

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Distortion of “tetrahedral” C3v coordination in the R3CO moiety due to the reduction of molecular symmetry: X-ray,. conformational, and quantum-chemical study

Cited by 40 publications

References 19 publications

Reducing GaH and GaC Bonds in Close Proximity to Oxidizing Peroxo Groups: Conflicting Properties in Single Molecules

Reducing GaH and GaC Bonds in Close Proximity to Oxidizing Peroxo Groups: Conflicting Properties in Single Molecules

Location of MTBE and toluene in the channel system of the zeolite mordenite: Adsorption and host–guest interactions

The Structural Chemistry of Acyclic Organic Peroxides

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