Epoxidation of cis-cyclooctene using diamine bis(phenolate) vanadium, molybdenum and tungsten complexes as catalysts

Filipe Madeira; Sónia Barroso; Sónia Namorado; Patricia M. Reis; Beatriz Royo; Ana Margarida Martins

doi:10.1016/j.ica.2011.10.071

Epoxidation of cis-cyclooctene using diamine bis(phenolate) vanadium, molybdenum and tungsten complexes as catalysts

Filipe Madeira, Sónia Barroso, Sónia Namorado, Patricia M. Reis, Beatriz Royo, Ana Margarida Martins

Instituto de Tecnologia Química e Biológica António Xavier (ITQB)

Research output: Contribution to journal › Article › peer-review

56 Citations (Scopus)

Abstract

The dioxomolybdenum and dioxotungsten complexes [MoO ₂L ¹] (1-Mo) and [WO ₂L ¹] (2-W), supported by a diamine bis(phenolate) ligand (L ¹ = Me ₂NCH ₂CH ₂N(CH ₂-2-O-3,5-C ₆H ₂ ^tBu ₂) ₂) were prepared from MoO ₂Cl ₂ and WO ₂Cl ₂(dme) in good yields. The solid-state structures of both compounds obtained by single crystal X-ray diffraction reveal distorted octahedral geometries around the metals with cis terminal oxo ligands. Their performance in the catalytic epoxidation of cis-cyclooctene using H ₂O ₂ and TBHP as oxidants was evaluated. 2-W displays high activity with H ₂O ₂ as terminal oxidant, achieving 84% conversion in 6 h (TOF = 1400 mol _sub mol _cat ^-1 h ^-1), while its molybdenum counterpart 1-Mo was inactive in the same conditions. Using TBHP as oxidant the opposite trend was observed and 1-Mo attained 93% conversion in 6 h (TOF = 1550 mol _sub mol _cat ^-1 h ^-1). The Oxovanadium complexes [VOL ¹Cl] (3-V), [VOL ²Cl] (4-V, L ² = Me ₂NCH ₂CH(CH ₃)N(CH ₂-2-O-3,5-C ₆H ₂ ^tBu ₂) ₂) and [(VOL ¹) ₂(μ-O)] (5-V) were also tested as catalysts in the epoxidation of cis-cyclooctene. The three compounds display high activity when the epoxidation reaction is performed using TBHP as oxidant. Using H ₂O ₂, 3-V and 4-V are moderately active while 5-V is inactive.

Original language	English
Pages (from-to)	152-156
Number of pages	5
Journal	Inorganica Chimica Acta
Volume	383
DOIs	https://doi.org/10.1016/j.ica.2011.10.071
Publication status	Published - 30 Mar 2012

Keywords

Diamine bis(phenolate) complexes
Epoxidation
Molybdenum
Tungsten
Vanadium

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10.1016/j.ica.2011.10.071

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@article{dd16c061571a4292adb37ff24952484a,

title = "Epoxidation of cis-cyclooctene using diamine bis(phenolate) vanadium, molybdenum and tungsten complexes as catalysts",

abstract = "The dioxomolybdenum and dioxotungsten complexes [MoO 2L 1] (1-Mo) and [WO 2L 1] (2-W), supported by a diamine bis(phenolate) ligand (L 1 = Me 2NCH 2CH 2N(CH 2-2-O-3,5-C 6H 2 tBu 2) 2) were prepared from MoO 2Cl 2 and WO 2Cl 2(dme) in good yields. The solid-state structures of both compounds obtained by single crystal X-ray diffraction reveal distorted octahedral geometries around the metals with cis terminal oxo ligands. Their performance in the catalytic epoxidation of cis-cyclooctene using H 2O 2 and TBHP as oxidants was evaluated. 2-W displays high activity with H 2O 2 as terminal oxidant, achieving 84\% conversion in 6 h (TOF = 1400 mol sub mol cat -1 h -1), while its molybdenum counterpart 1-Mo was inactive in the same conditions. Using TBHP as oxidant the opposite trend was observed and 1-Mo attained 93\% conversion in 6 h (TOF = 1550 mol sub mol cat -1 h -1). The Oxovanadium complexes [VOL 1Cl] (3-V), [VOL 2Cl] (4-V, L 2 = Me 2NCH 2CH(CH 3)N(CH 2-2-O-3,5-C 6H 2 tBu 2) 2) and [(VOL 1) 2(μ-O)] (5-V) were also tested as catalysts in the epoxidation of cis-cyclooctene. The three compounds display high activity when the epoxidation reaction is performed using TBHP as oxidant. Using H 2O 2, 3-V and 4-V are moderately active while 5-V is inactive.",

keywords = "Diamine bis(phenolate) complexes, Epoxidation, Molybdenum, Tungsten, Vanadium",

author = "Filipe Madeira and S{\'o}nia Barroso and S{\'o}nia Namorado and Reis, \{Patricia M.\} and Beatriz Royo and Martins, \{Ana Margarida\}",

note = "The authors thank the Portuguese NMR Network (IST-UTL Center) for providing access to the NMR facilities and the Fundacao para a Ciencia e Tecnologia for financial support (research projects PTDC/QUI/66187/2006 and PTDC/QUI/098682/2008 and fellowships SFRH/BD/13374/2003, SFRH/BP/20655/2004 and SFRH/BD/28762/2006).",

year = "2012",

month = mar,

day = "30",

doi = "10.1016/j.ica.2011.10.071",

language = "English",

volume = "383",

pages = "152--156",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier",

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TY - JOUR

T1 - Epoxidation of cis-cyclooctene using diamine bis(phenolate) vanadium, molybdenum and tungsten complexes as catalysts

AU - Madeira, Filipe

AU - Barroso, Sónia

AU - Namorado, Sónia

AU - Reis, Patricia M.

AU - Royo, Beatriz

AU - Martins, Ana Margarida

N1 - The authors thank the Portuguese NMR Network (IST-UTL Center) for providing access to the NMR facilities and the Fundacao para a Ciencia e Tecnologia for financial support (research projects PTDC/QUI/66187/2006 and PTDC/QUI/098682/2008 and fellowships SFRH/BD/13374/2003, SFRH/BP/20655/2004 and SFRH/BD/28762/2006).

PY - 2012/3/30

Y1 - 2012/3/30

N2 - The dioxomolybdenum and dioxotungsten complexes [MoO 2L 1] (1-Mo) and [WO 2L 1] (2-W), supported by a diamine bis(phenolate) ligand (L 1 = Me 2NCH 2CH 2N(CH 2-2-O-3,5-C 6H 2 tBu 2) 2) were prepared from MoO 2Cl 2 and WO 2Cl 2(dme) in good yields. The solid-state structures of both compounds obtained by single crystal X-ray diffraction reveal distorted octahedral geometries around the metals with cis terminal oxo ligands. Their performance in the catalytic epoxidation of cis-cyclooctene using H 2O 2 and TBHP as oxidants was evaluated. 2-W displays high activity with H 2O 2 as terminal oxidant, achieving 84% conversion in 6 h (TOF = 1400 mol sub mol cat -1 h -1), while its molybdenum counterpart 1-Mo was inactive in the same conditions. Using TBHP as oxidant the opposite trend was observed and 1-Mo attained 93% conversion in 6 h (TOF = 1550 mol sub mol cat -1 h -1). The Oxovanadium complexes [VOL 1Cl] (3-V), [VOL 2Cl] (4-V, L 2 = Me 2NCH 2CH(CH 3)N(CH 2-2-O-3,5-C 6H 2 tBu 2) 2) and [(VOL 1) 2(μ-O)] (5-V) were also tested as catalysts in the epoxidation of cis-cyclooctene. The three compounds display high activity when the epoxidation reaction is performed using TBHP as oxidant. Using H 2O 2, 3-V and 4-V are moderately active while 5-V is inactive.

AB - The dioxomolybdenum and dioxotungsten complexes [MoO 2L 1] (1-Mo) and [WO 2L 1] (2-W), supported by a diamine bis(phenolate) ligand (L 1 = Me 2NCH 2CH 2N(CH 2-2-O-3,5-C 6H 2 tBu 2) 2) were prepared from MoO 2Cl 2 and WO 2Cl 2(dme) in good yields. The solid-state structures of both compounds obtained by single crystal X-ray diffraction reveal distorted octahedral geometries around the metals with cis terminal oxo ligands. Their performance in the catalytic epoxidation of cis-cyclooctene using H 2O 2 and TBHP as oxidants was evaluated. 2-W displays high activity with H 2O 2 as terminal oxidant, achieving 84% conversion in 6 h (TOF = 1400 mol sub mol cat -1 h -1), while its molybdenum counterpart 1-Mo was inactive in the same conditions. Using TBHP as oxidant the opposite trend was observed and 1-Mo attained 93% conversion in 6 h (TOF = 1550 mol sub mol cat -1 h -1). The Oxovanadium complexes [VOL 1Cl] (3-V), [VOL 2Cl] (4-V, L 2 = Me 2NCH 2CH(CH 3)N(CH 2-2-O-3,5-C 6H 2 tBu 2) 2) and [(VOL 1) 2(μ-O)] (5-V) were also tested as catalysts in the epoxidation of cis-cyclooctene. The three compounds display high activity when the epoxidation reaction is performed using TBHP as oxidant. Using H 2O 2, 3-V and 4-V are moderately active while 5-V is inactive.

KW - Diamine bis(phenolate) complexes

KW - Epoxidation

KW - Molybdenum

KW - Tungsten

KW - Vanadium

UR - https://www.scopus.com/pages/publications/84857233764

U2 - 10.1016/j.ica.2011.10.071

DO - 10.1016/j.ica.2011.10.071

M3 - Article

AN - SCOPUS:84857233764

SN - 0020-1693

VL - 383

SP - 152

EP - 156

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Epoxidation of cis-cyclooctene using diamine bis(phenolate) vanadium, molybdenum and tungsten complexes as catalysts

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Keywords

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