Untersuchungen über Metallalkoholate und Orthosäureester. I. Über Alkoxosäuren und ihre Salze

Meerwein, Hans; Bersin, Theodor

doi:10.1002/jlac.19294760105

Cited by 126 publications

(40 citation statements)

References 14 publications

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“…This is in contrast to the reaction of Te(OiPr) 4 with HOCH 2 CH 2 NMe 2 , where all OiPr groups could be substituted by OCH 2 CH 2 NMe 2 groups, leading to compound 2. Thus, the conclusion could be drawn that the nucleophilic substitution reactions with the Te atoms in TeCl 4 and Te(OiPr) 4 proceed with different mechanisms and that the intramolecular Te···N interactions in 1a and 4a exhibit different strengths (see also the ab initio studies below). For TeCl 4 , an associative-dissociative mechanism (Scheme 2) is assumed, whereas for Te(OiPr) 4 a dissociative-associative mechanism (Scheme 3) is more likely.…”

Section: Resultsmentioning

confidence: 75%

“…[1] In order to obtain tellurium(IV) tetraalkoxides, Te(OR) 4 , from TeCl 4 and the appropriate alcohol, HOR, the latter has to be activated. This activation can either be achieved by O-silylation or O-metallation of the alcohol prior to the synthesis or by addition of tertiary amines which drive the reaction by formation of the corresponding ammonium chloride.…”

Section: Introductionmentioning

confidence: 99%

“…This activation can either be achieved by O-silylation or O-metallation of the alcohol prior to the synthesis or by addition of tertiary amines which drive the reaction by formation of the corresponding ammonium chloride. [2Ϫ4] Alternatively, Te(OR) 4 can be derived from Te(ORЈ) 4 and HOR by ligand exchange according to Equation (1). [ 3 OCH 2 CH 2 XH n (1α−1γ) as well as an analysis of the bonds in terms of natural bond orbitals were performed in order to study the nature of the Te···X bond and its dependence on conformational restraints.…”

Section: Introductionmentioning

confidence: 99%

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Tellurium(IV) Tetraalkoxides and Chlorotellurium(IV) Alkoxides Derived from β-Donor Alcohols

Fleischer

Dienes

Schollmeyer

2002

Eur. J. Inorg. Chem.

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Keywords: Tellurium / Donor-acceptor systems / Ab initio calculations / X-ray diffraction / NMR spectroscopy Te(OiPr) 3 OCH 2 CH 2 XMe n (1a−1c) and Te(OCH 2 CH 2 NMe 2 ) 4 (2) were synthesised by the reaction of Te(OiPr) 4 with HOCH 2 CH 2 XMe n , while TeCl 2 (OCH 2 CH 2 OMe) 2 (3) and TeCl 3 OCH 2 CH 2 XMe n (4a−4c) resulted from the reaction of TeCl 4 with the corresponding silylated alcohols Me 3 Si-OCH 2 CH 2 XMe n (X = N, n = 2; X = O or S, n = 1). These compounds are the first known representatives of the hitherto unknown classes of tellurium(IV) tetraalkoxides and chlorotellurium(IV) alkoxides derived from β-donor-substituted alcohols. The donor atom X in the alkoxy ligand enables an intramolecular donor-acceptor Te···X interaction, which stabilises the di-and trichlorotellurium alkoxides, but reduces the reactivity of the tellurium atom towards nucleophiles, a result from which an associative-dissociative mechanism was inferred for the nucleophilic substitution in TeCl 4 . In contrast to this, all OiPr ligands of Te(OiPr) 4 can be exchanged by reaction with HOCH 2 CH 2 XMe n . As was shown by multinuclear NMR studies, the kinetics and equilibrium of the reaction of Te(OiPr) 4 with HOCH 2 CH 2 XMe n depend substantially on X and thus demonstrate the presence of Te···X interactions in solution. The molecular and crystal structure of 3 was investigated by single-crystal X-ray diffraction. In the solid state of 3, two kinds of molecules are

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Section: Resultsmentioning

confidence: 75%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Tellurium(IV) Tetraalkoxides and Chlorotellurium(IV) Alkoxides Derived from β-Donor Alcohols

Fleischer

Dienes

Schollmeyer

2002

Eur. J. Inorg. Chem.

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“…Tetraalkoxytelluranes have been prepared by the condensation of tellurium tetrachloride with sodium alkoxides in the presence of excess alcohols (13). Aromatic (14) and aliphatic ( 15) diols have also been reported to condense with tellurium dioxide or telluric acid to give the corresponding tetraalkoxytelluranes.…”

Section: Resultsmentioning

confidence: 99%

Chalcogenide esters as reactive intermediates in selenium and tellurium purifications

Badesha¹,

Monczka²,

Smith³

1983

Can. J. Chem.

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This paper describes a novel application of chalcogenide esters to purify selenium and tellurium to the 99.999% purity level. The chalcogenide esters were prepared from a variety of source materials which include: crude selenium and tellurium and commercial grade selenium dioxide, tellurium dioxide, and selenous acid. Crude selenium and tellurium were first converted to their respective oxides by treatment with concentrated nitric acid. The oxides were condensed with alcohols or diols to obtain the corresponding esters which, on reduction with hydrazine in organic media, provided high purity elemental selenium and tellurium.

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“…Die Ansa È tze reichen von Vorstufen zur Al 2 O 3 -Bildung [3] bis zur Verwendung in der organischen Synthese [4,5]. Der Grundstein fu È r den Erfolg wurde aber schon in der Pionierarbeit von Meerwein und Bersin gelegt [6], in welcher auch schon erste Ansa È tze zur Ûbertragung von Alkoxyfunktionen auf andere Metallzentren vorgestellt wurden. Ausfu È hrliche Untersuchungen erfolgten spa È ter von Mehrotra et al [7] und Veith et al [8].…”

Section: Introductionunclassified

Synthesen und Reaktionen von Aluminiumalkoxid-Verbindungen

Pauls

Neumüller

2000

Z. anorg. allg. Chem.

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Untersuchungen über Metallalkoholate und Orthosäureester. I. Über Alkoxosäuren und ihre Salze

Cited by 126 publications

References 14 publications

Tellurium(IV) Tetraalkoxides and Chlorotellurium(IV) Alkoxides Derived from β-Donor Alcohols

Tellurium(IV) Tetraalkoxides and Chlorotellurium(IV) Alkoxides Derived from β-Donor Alcohols

Chalcogenide esters as reactive intermediates in selenium and tellurium purifications

Synthesen und Reaktionen von Aluminiumalkoxid-Verbindungen

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