Molybdenum and tungsten (VI) bimetallic alkoxides. Decomposition accompanied by dialkylether elimination

Turova, Nataliya; Kessler, Vadim G.; Kucheiko, S.I.

doi:10.1016/s0277-5387(00)81337-6

Cited by 85 publications

(39 citation statements)

References 24 publications

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“…The tungsten compounds W 16 O 2 (L) and W 18 O 2 (L) used in this study were prepared following the known procedure, i. e. by the reaction of W(eg) 3 (eg=ethylene glycolate dianion) with the ligand precursor in the presence of H 2 [ 16 O] or H 2 [ 18 O] (Scheme a). In principle, the formation of a WO 2 2+ moiety using trisglycolate precursor may be due to the ether elimination process of the alkoxide groups, or by hydrolysis. The mass and IR spectra (see below) show that the addition of either H 2 [ 16 O] or H 2 [ 18 O] in the reaction mixture leads to the clean formation of the respective isotopologue which demonstrates that the formation of dioxidotungsten centre is caused by the hydrolysis reaction wherein the included water acts as the oxide source.…”

Section: Resultsmentioning

confidence: 99%

“…However, the origin of these terminal oxido ligands in the reactions of a trisglycolate precursor is not unambiguous. Water is the most likely source of the oxo‐groups, but, on the other hand, it is known that high‐valent molybdenum, tungsten and rhenium alkoxides can decompose by an elimination process, which yields an ether and the corresponding oxidometal species ,. We decided to investigate the mechanism of the formation of the oxido species by reacting W(eg) 3 with an amine bisphenol ligand in the presence of either H 2 [ 16 O] or H 2 [ 18 O] to form a dioxido complex WO 2 (L).…”

Section: Introductionmentioning

confidence: 99%

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The Syntheses and Vibrational Spectra of ¹⁶O‐ and ¹⁸O‐Enriched cis‐MO₂ (M=Mo, W) Complexes

2018

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In this contribution, we report convenient synthetic approaches for obtaining 16O/18O‐enriched dioxidometalVI complexes, MO2(L) (W, Mo), with a linear, tetradentate amine phenolate ligand N,N′‐dimethyl‐N,N′‐bis(2‐hydroxy‐3,5‐dimethylbenzyl)ethylenediamine (H2L) and describe their characterization by IR and Raman spectroscopy complemented by DFT computational analysis. The isotopologues of WO2(L) were made of tungstenVI trisglycolate W(eg)3 (eg=1,2‐ethanediolate dianion) and ligand H2L in the presence of either H2[16O] or H2[18O], whereas Mo16O2(L) was made using Na2MoO4⋅2H2O which was converted to Mo18O2(L) by oxido substitution using H2[18O]. The complementary IR and Raman analyses show the ν(MO2)s and ν(MO2)a at 934 and 899 cm–1 for W16O2(L) and at 914 and 898 cm–1 for Mo16O2(L), respectively. In the vibrational spectra of the 18O substituted derivatives, the ν(MO2)s were shifted to lower energy by 43 cm–1 for W18O2(L) and by 41 cm–1 for Mo18O2(L) whereas asymmetric MO2 stretches in the IR were partially overlapped by an organic ligand related stretch. However, Raman spectroscopy, accompanied by DFT calculations, allowed the deciphering the ν(MO2)a shifts of 47 cm–1 for W18O2(L) and 31 cm–1 for Mo18O2(L).

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Syntheses and Vibrational Spectra of ¹⁶O‐ and ¹⁸O‐Enriched cis‐MO₂ (M=Mo, W) Complexes

2018

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“…Turova et al. reported the release of diethyl ether from an alcohol solution containing MoO(OEt) 4 in the presence of pronouncedly basic lithium and sodium ethoxides, resulting in the precipitation of Li 2 MoO 4 and Na 2 MoO 4 . Kessler et al.…”

Section: Chemical Formation Mechanismsmentioning

confidence: 99%

Mechanistic Aspects in the Formation, Growth and Surface Functionalization of Metal Oxide Nanoparticles in Organic Solvents

Deshmukh

Niederberger

2017

Chemistry A European J

112

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The synthesis of metal oxide nanoparticles in organic solvents, so-called nonaqueous (or nonhydrolytic) processes represent powerful alternatives to aqueous approaches and have become an independent research field. 10 Years ago, when we published our first review on organic reaction pathways in nonaqueous sol-gel approaches, the number of examples was relatively limited. Nowadays, it is almost impossible to provide an exhaustive overview. Here we review the development of the last few years, without neglecting pioneering examples, which help to follow the historical development. The importance of a profound understanding of mechanistic aspects of nanoparticle crystallization and formation mechanisms can't be overestimated, when it comes to the design of rational synthesis concepts under minimization of trial-and-error experiments. The main reason for the progress in mechanistic understanding lies in the availability of characterization tools that make it possible to monitor chemical reactions from the dissolution of the precursor to the nucleation and growth of the nanoparticles, by ex situ methods involving sampling after different reaction times, but more and more also by in situ studies. After a short introduction to experimental aspects of nonaqueous sol-gel routes to metal oxide nanoparticles, we provide an overview of the main and basic organic reaction pathways in these approaches. Afterwards, we summarize the main characterization methods to study formation mechanisms, and then we discuss in great depth the chemical formation mechanisms of many different types of metal oxide nanoparticles. The review concludes with a paragraph on selected crystallization mechanisms reported for nonaqueous systems and a few illustrative examples of nonaqueous sol-gel concepts applied to surface chemistry.

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“…This reaction principle was later utilized for the synthesis of other oxide-alkoxide molecular species (Ti, Ba-Mo, Na-W, Na-Mo, etc.) [158][159][160], polyoxovanadate and molybdate clusters [161] and finally for the preparation of metal oxide nanoparticles [56,162,163]. The synthesis was often performed in alcoholic solutions as the protic solvent facilitates the condensation [56].…”

Section: Ether Eliminationmentioning

confidence: 99%

The Power of Non-Hydrolytic Sol-Gel Chemistry: A Review

et al. 2017

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This review is devoted to non-hydrolytic sol-gel chemistry. During the last 25 years, non-hydrolytic sol-gel (NHSG) techniques were found to be attractive and versatile methods for the preparation of oxide materials. Compared to conventional hydrolytic approaches, the NHSG route allows reaction control at the atomic scale resulting in homogeneous and well defined products. Due to these features and the ability to design specific materials, the products of NHSG reactions have been used in many fields of application. The aim of this review is to present an overview of NHSG research in recent years with an emphasis on the syntheses of mixed oxides, silicates and phosphates. The first part of the review highlights well known condensation reactions with some deeper insights into their mechanism and also presents novel condensation reactions established in NHSG chemistry in recent years. In the second section we discuss porosity control and novel compositions of selected materials. In the last part, the applications of NHSG derived materials as heterogeneous catalysts and supports, luminescent materials and electrode materials in Li-ion batteries are described.

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Molybdenum and tungsten (VI) bimetallic alkoxides. Decomposition accompanied by dialkylether elimination

Cited by 85 publications

References 24 publications

The Syntheses and Vibrational Spectra of ¹⁶O‐ and ¹⁸O‐Enriched cis‐MO₂ (M=Mo, W) Complexes

The Syntheses and Vibrational Spectra of ¹⁶O‐ and ¹⁸O‐Enriched cis‐MO₂ (M=Mo, W) Complexes

Mechanistic Aspects in the Formation, Growth and Surface Functionalization of Metal Oxide Nanoparticles in Organic Solvents

The Power of Non-Hydrolytic Sol-Gel Chemistry: A Review

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Molybdenum and tungsten (VI) bimetallic alkoxides. Decomposition accompanied by dialkylether elimination

Cited by 85 publications

References 24 publications

The Syntheses and Vibrational Spectra of 16O‐ and 18O‐Enriched cis‐MO2 (M=Mo, W) Complexes

The Syntheses and Vibrational Spectra of 16O‐ and 18O‐Enriched cis‐MO2 (M=Mo, W) Complexes

Mechanistic Aspects in the Formation, Growth and Surface Functionalization of Metal Oxide Nanoparticles in Organic Solvents

The Power of Non-Hydrolytic Sol-Gel Chemistry: A Review

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The Syntheses and Vibrational Spectra of ¹⁶O‐ and ¹⁸O‐Enriched cis‐MO₂ (M=Mo, W) Complexes

The Syntheses and Vibrational Spectra of ¹⁶O‐ and ¹⁸O‐Enriched cis‐MO₂ (M=Mo, W) Complexes