A 5-(2-Pyridyl)tetrazolate Complex of Molybdenum(VI), Its Structure, and Transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins

There is a considerable practical interest in discovering new ways to obtain organomolybdenum heterogeneous catalysts for olefin epoxidation that are easier to recover and reuse and display enhanced productivity. In this study, the complex salt (H<sub>2</sub>pytz)[MoO<sub>2</sub...

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Autores principales:	Martinique S. Nunes, Diana M. Gomes, Ana C. Gomes, Patrícia Neves, Ricardo F. Mendes, Filipe A. Almeida Paz, André D. Lopes, Anabela A. Valente, Isabel S. Gonçalves, Martyn Pillinger
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	molybdenum molybdenum oxide organic-inorganic hybrid material tetrazole 5-(2-pyridyl)tetrazole hydrogen bonds Chemical technology TP1-1185 Chemistry QD1-999
Acceso en línea:	https://doaj.org/article/97a92e97a0b74a24ae9ca8718ac10177
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spelling	oai:doaj.org-article:97a92e97a0b74a24ae9ca8718ac101772021-11-25T17:06:53ZA 5-(2-Pyridyl)tetrazolate Complex of Molybdenum(VI), Its Structure, and Transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins10.3390/catal111114072073-4344https://doaj.org/article/97a92e97a0b74a24ae9ca8718ac101772021-11-01T00:00:00Zhttps://www.mdpi.com/2073-4344/11/11/1407https://doaj.org/toc/2073-4344There is a considerable practical interest in discovering new ways to obtain organomolybdenum heterogeneous catalysts for olefin epoxidation that are easier to recover and reuse and display enhanced productivity. In this study, the complex salt (H<sub>2</sub>pytz)[MoO<sub>2</sub>Cl<sub>2</sub>(pytz)] (<b>1</b>) (Hpytz = 5-(2-pyridyl)tetrazole) has been prepared, structurally characterized, and employed as a precursor for the hydrolysis-based synthesis of a microcrystalline molybdenum oxide/organic hybrid material formulated as [MoO<sub>3</sub>(Hpytz)] (<b>2</b>). In addition to single-crystal X-ray diffraction (for <b>1</b>), compounds <b>1</b> and <b>2</b> were characterized by FT-IR and Raman spectroscopies, solid-state <sup>13</sup>C{<sup>1</sup>H} cross-polarization (CP) magic-angle spinning (MAS) NMR, and scanning electron microscopy (SEM). Compounds <b>1</b> and <b>2</b> were evaluated as olefin epoxidation catalysts using the model reaction of <i>cis</i>-cyclooctene (Cy8) with <i>tert</i>-butyl hydroperoxide (TBHP), at 70 °C, which gave 100% epoxide selectivity up to 100% conversion. While <b>1</b> behaved as a homogeneous catalyst, hybrid <b>2</b> behaved as a heterogeneous catalyst and could be recovered for recycling without showing structural degradation or loss of catalytic performance over consecutive reaction cycles. The substrate scope was broadened to monoterpene <i>DL</i>-limonene (Lim) and biobased unsaturated fatty acid methyl esters, methyl oleate (MeOle), and methyl linoleate (MeLin), which gave predominantly epoxide products.Martinique S. NunesDiana M. GomesAna C. GomesPatrícia NevesRicardo F. MendesFilipe A. Almeida PazAndré D. LopesAnabela A. ValenteIsabel S. GonçalvesMartyn PillingerMDPI AGarticlemolybdenummolybdenum oxideorganic-inorganic hybrid materialtetrazole5-(2-pyridyl)tetrazolehydrogen bondsChemical technologyTP1-1185ChemistryQD1-999ENCatalysts, Vol 11, Iss 1407, p 1407 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	molybdenum molybdenum oxide organic-inorganic hybrid material tetrazole 5-(2-pyridyl)tetrazole hydrogen bonds Chemical technology TP1-1185 Chemistry QD1-999
spellingShingle	molybdenum molybdenum oxide organic-inorganic hybrid material tetrazole 5-(2-pyridyl)tetrazole hydrogen bonds Chemical technology TP1-1185 Chemistry QD1-999 Martinique S. Nunes Diana M. Gomes Ana C. Gomes Patrícia Neves Ricardo F. Mendes Filipe A. Almeida Paz André D. Lopes Anabela A. Valente Isabel S. Gonçalves Martyn Pillinger A 5-(2-Pyridyl)tetrazolate Complex of Molybdenum(VI), Its Structure, and Transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
description	There is a considerable practical interest in discovering new ways to obtain organomolybdenum heterogeneous catalysts for olefin epoxidation that are easier to recover and reuse and display enhanced productivity. In this study, the complex salt (H<sub>2</sub>pytz)[MoO<sub>2</sub>Cl<sub>2</sub>(pytz)] (<b>1</b>) (Hpytz = 5-(2-pyridyl)tetrazole) has been prepared, structurally characterized, and employed as a precursor for the hydrolysis-based synthesis of a microcrystalline molybdenum oxide/organic hybrid material formulated as [MoO<sub>3</sub>(Hpytz)] (<b>2</b>). In addition to single-crystal X-ray diffraction (for <b>1</b>), compounds <b>1</b> and <b>2</b> were characterized by FT-IR and Raman spectroscopies, solid-state <sup>13</sup>C{<sup>1</sup>H} cross-polarization (CP) magic-angle spinning (MAS) NMR, and scanning electron microscopy (SEM). Compounds <b>1</b> and <b>2</b> were evaluated as olefin epoxidation catalysts using the model reaction of <i>cis</i>-cyclooctene (Cy8) with <i>tert</i>-butyl hydroperoxide (TBHP), at 70 °C, which gave 100% epoxide selectivity up to 100% conversion. While <b>1</b> behaved as a homogeneous catalyst, hybrid <b>2</b> behaved as a heterogeneous catalyst and could be recovered for recycling without showing structural degradation or loss of catalytic performance over consecutive reaction cycles. The substrate scope was broadened to monoterpene <i>DL</i>-limonene (Lim) and biobased unsaturated fatty acid methyl esters, methyl oleate (MeOle), and methyl linoleate (MeLin), which gave predominantly epoxide products.
format	article
author	Martinique S. Nunes Diana M. Gomes Ana C. Gomes Patrícia Neves Ricardo F. Mendes Filipe A. Almeida Paz André D. Lopes Anabela A. Valente Isabel S. Gonçalves Martyn Pillinger
author_facet	Martinique S. Nunes Diana M. Gomes Ana C. Gomes Patrícia Neves Ricardo F. Mendes Filipe A. Almeida Paz André D. Lopes Anabela A. Valente Isabel S. Gonçalves Martyn Pillinger
author_sort	Martinique S. Nunes
title	A 5-(2-Pyridyl)tetrazolate Complex of Molybdenum(VI), Its Structure, and Transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
title_short	A 5-(2-Pyridyl)tetrazolate Complex of Molybdenum(VI), Its Structure, and Transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
title_full	A 5-(2-Pyridyl)tetrazolate Complex of Molybdenum(VI), Its Structure, and Transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
title_fullStr	A 5-(2-Pyridyl)tetrazolate Complex of Molybdenum(VI), Its Structure, and Transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
title_full_unstemmed	A 5-(2-Pyridyl)tetrazolate Complex of Molybdenum(VI), Its Structure, and Transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
title_sort	5-(2-pyridyl)tetrazolate complex of molybdenum(vi), its structure, and transformation to a molybdenum oxide-based hybrid heterogeneous catalyst for the epoxidation of olefins
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/97a92e97a0b74a24ae9ca8718ac10177
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A 5-(2-Pyridyl)tetrazolate Complex of Molybdenum(VI), Its Structure, and Transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins

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