Oxidomolybdenum(VI) complexes with aminoalcohol bis(phenolate) [O,N,O,O′] ligands: Synthesis and catalytic studies

Hakala, Juuso O; Sillanpää, Reijo; Lehtonen, Ari

doi:10.1016/j.inoche.2012.03.043

Cited by 10 publications

(10 citation statements)

References 13 publications

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“…The nitrogen donor is located trans to the terminal oxo, which is typical for oxomolybdenum aminophenolates [3][4][5][6][7][21][22][23][24]. Otherwise, the bonding parameters between the metal center and the trianionic aminocarboxylate bisphenolate ligand are in accord with previous studies on oxomolybdenum(VI) complexes with tripodal aminoalcohol bisphenolates and amine trisphenolates [3,4,21,26]. 2.43 Å) due to the strong structural trans effect of a multiple bonded oxo ligand [25].…”

Section: Structure Descriptionsupporting

confidence: 86%

“…Under such conditions, the reaction leads to a mixture of several compounds as seen by TLC. Generally, these carboxylate complexes, cis-1 and trans-1, are less stable than corresponding aminoalkoxide bisphenolates [4,21]. 1 : 1 ratio.…”

Section: Synthesismentioning

confidence: 95%

“…In solid state, it forms monomeric molecules in which the glycine bisphenolate has Oxomolybdenum(VI) complexes 1867 coordinated as a tetradentate trianionic ligand through three oxygen donors and one nitrogen donor (figure 1). 0.11 Å longer than Mo-O alkoxide (1.897-1.903 Å) [4,21] or aryloxide (1.873-1.903 Å) [3,25] bonds in structurally related aminoalcoholate bisphenolates or amine trisphenolates. The Mo-N bond is relatively long (ca.…”

Section: Structure Descriptionmentioning

confidence: 95%

“…The nitrogen donor is located trans to the terminal oxo, which is typical for oxomolybdenum aminophenolates [3][4][5][6][7][21][22][23][24]. In solid state, it forms monomeric molecules in which the glycine bisphenolate has Oxomolybdenum(VI) complexes 1867 coordinated as a tetradentate trianionic ligand through three oxygen donors and one nitrogen donor (figure 1).…”

Section: Structure Descriptionmentioning

confidence: 99%

“…Synthetic approaches to model the active sites of molybdenum enzymes have been either biomimetic (structural modeling) or bioinspired (functional modeling), and rather simple coordination compounds can be studied as models for sophisticated biological systems [2]. For example, the reactions of MoO 2 Cl 2 derivatives with tetrapodal amine trisphenols or aminoalcohol bisphenols are known to lead to neutral mononuclear oxochloromolybdenum(VI) complexes which can catalyze a number of oxidations including sulfoxidation, epoxidation, and haloperoxidation reactions [3,4]. Multidentate phenolic ligands are generally used to make such model compounds.…”

Section: Introductionmentioning

confidence: 99%

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Oxomolybdenum(VI) complexes with glycine bisphenol [O,N,O,O′] ligand: synthesis and catalytic studies

Heikkilä

Sillanpää

Lehtonen

2014

Journal of Coordination Chemistry

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The oxomolybdenum(VI) complex [MoOCl(L)] with a tetradentate glycine bisphenol ligand (H 3 L) was prepared by reaction of [MoO 2 Cl 2 (DMSO) 2 ] with a ligand precursor in hot toluene. The product was isolated in moderate yield as separable cis and trans isomers along with the third minor component, [MoO 2 (HL)]. The solid-state structure of trans-[MoOCl(L)] was determined by X-ray diffraction. The ligand has tetradentate coordination through three oxygens and one nitrogen, which is located trans to the terminal oxo whereas the sixth coordination site is occupied by a chloride. Both cis and trans isomers of [MoOCl(L)] are active catalysts for epoxidation of cis-cyclooctene and sulfoxidation of tolyl methyl sulfide. The cis isomer gave higher activity in epoxidation and sulfoxidation reactions at room temperature than the trans isomer but they performed identically at 50°C.

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Section: Structure Descriptionsupporting

confidence: 86%

Section: Synthesismentioning

confidence: 95%

Section: Structure Descriptionmentioning

confidence: 95%

Section: Structure Descriptionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Oxomolybdenum(VI) complexes with glycine bisphenol [O,N,O,O′] ligand: synthesis and catalytic studies

Heikkilä

Sillanpää

Lehtonen

2014

Journal of Coordination Chemistry

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Advances in the Catalysis of Organic Processes by Metal Phenolates

Serra

Murtinho

2016

Patai's Chemistry of Functional Groups

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Transition‐metal catalysts with phenolate ligands comprise a great variety of compounds with appropriate characteristics capable of promoting numerous reactions of extreme importance in synthetic organic chemistry. Included in these transformations are oxidations of alkenes, sulfides, alcohols, and alkanes, cyanations, alkynylations, alkylations, hydroaminations, and nitroaldol reactions. An extensive review of the catalysis of organic processes by metal phenolates has been presented in a previous volume of this series. This chapter is an update of the advances published from 2011 to the beginning of 2015, with emphasis on the type of reactions catalyzed by metal phenolates that have gained more attention in the literature during this period.

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Dioxomolybdenum(VI) and ‐tungsten(VI) Complexes with Multidentate Aminobisphenol Ligands as Catalysts for Olefin Epoxidation

et al. 2015

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The synthesis of four molybdenum and tungsten complexes bearing tetradentate tripodal amino bisphenolate ligands with either hydroxyethylene (1a) or hydroxyglycolene (1b) substituents is reported. The molybdenum dioxo complexes [MoO2L] (L = 2a, 2b) and tungsten complexes [WO2L] (3a, 3b) were synthesized using [MoO2(acac)2] and [W(eg)3] (eg = 1,2‐ethanediolato, ethylene glycolate), respectively, as precursors. All complexes were characterized by spectroscopic means as well as by single‐crystal X‐ray diffraction analyses. The latter reveal, in all cases, hexacoordinate complexes in which the hydrogen atom of the hydroxy group is involved in hydrogen bonding with one of the metal oxo groups. In the case of the glycol substituent, the ether oxygen atom is coordinated to the metal whereas the hydroxy group remains uncoordinated. The complexes were tested as catalysts in the epoxidation of cyclooctene under eco‐friendly conditions, using an aqueous solution of H2O2 as the oxidant and dimethyl carbonate (DMC) as solvent or neat conditions, as substitutes for chlorinated solvents. Molybdenum complexes 2a and 2b showed good catalytic activity using H2O2 without added solvent, and tungsten complexes 3a and 3b showed very high activity in the epoxidation of cyclooctene using H2O2 and DMC as solvents.

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Oxidomolybdenum(VI) complexes with aminoalcohol bis(phenolate) [O,N,O,O′] ligands: Synthesis and catalytic studies

Cited by 10 publications

References 13 publications

Oxomolybdenum(VI) complexes with glycine bisphenol [O,N,O,O′] ligand: synthesis and catalytic studies

Oxomolybdenum(VI) complexes with glycine bisphenol [O,N,O,O′] ligand: synthesis and catalytic studies

Advances in the Catalysis of Organic Processes by Metal Phenolates

Dioxomolybdenum(VI) and ‐tungsten(VI) Complexes with Multidentate Aminobisphenol Ligands as Catalysts for Olefin Epoxidation

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