The Synthesis, Structures and Characterisation of New Mixed‐Ligand Manganese and Iron Complexes with Tripodal, Tetradentate Ligands

Gorkum, Remy van; Berding, Joris; Mills, Allison M.; Kooijman, Huub; Tooke, Duncan M.; Spek, Anthony L.; Mutikainen, Ilpo; Turpeinen, Urho; Reedijk, Jan; Bouwman, Elisabeth

doi:10.1002/ejic.200701280

Cited by 29 publications

(38 citation statements)

References 45 publications

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“…1. The Mn(III) ion in IV has a distorted octahedral coordination geometry, just as the other [Mn(III)(tripod)(β-diketonate)] complexes reported earlier [18]. In contrast with the pppy-complexes Ia, Ic, and Id, however, complex IV has both oxygen donor atoms of the acac ligand (O202 and O201) in the equatorial plane, together with the amine nitrogen atom N101 and the phenolate oxygen atom O101.…”

Section: Synthesis and Characterisation Of Potential Drier Complexesmentioning

confidence: 58%

“…The Jahn-Teller axis of the d 4 Mn(III) ion is located along the bonds Mn1-N(pyridine) and Mn1-O(carboxylate). The N(pyridine)-Mn1 bond length is slightly longer than observed for the other [Mn(III)(tripod)(β-diketonate)] complexes [18]. The bond lengths of the phenolate oxygen and the amine nitrogen to the manganese center are both comparable to those in the Ia, Ic, and Id complexes.…”

Section: Synthesis and Characterisation Of Potential Drier Complexesmentioning

confidence: 62%

“…The complex [Mn(III)(acac) 3 ] was prepared as described previously [21]. The synthesis and characterisation of the complexes with the tripodal ligands H 2 pppy, H 2 tbpppy, and H 2 dnpppy have been reported elsewhere [18].…”

Section: Methodsmentioning

confidence: 99%

“…The synthesis, spectroscopic characterisation, and structures of the complexes I-III have been described elsewhere [18]. For the complex [Mn(papy)(acac)] (IV), single crystals were obtained, and the crystal structure was determined.…”

Section: Synthesis and Characterisation Of Potential Drier Complexesmentioning

confidence: 99%

“…β-Diketonates were chosen as the "secondary" ligand because good autoxidation results have been obtained with simple, homoleptic manganese β-diketonate complexes [7,8]. We have synthesised and characterised a series of manganese(III) and iron(III) coordination compounds with one dianionic tripodal ligand and one auxiliary ligand (Schemes 1 and 2) [18]. The resulting complexes are noncharged, which is expected to result in good solubility in apolar solvents.…”

Section: Introductionmentioning

confidence: 99%

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The autoxidation activity of new mixed-ligand manganese and iron complexes with tripodal ligands

Gorkum

Berding

Tooke

et al. 2007

Journal of Catalysis

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The activity of new manganese and iron complexes of dianionic tripodal ligands in the autoxidation of ethyl linoleate (EL) is reported. EL consumption rates were monitored using time-resolved FTIR and the degree of oligomerisation was determined by SEC. Almost all complexes showed the same trend in the autoxidation of EL. After a short induction time, the reaction started at a relatively high constant rate; later, this rate changes to a lower rate, which was again constant and on average was the same for all complexes studied. The observation that the autoxidation rate eventually became the same for all complexes can be explained with the assumption that a catalytic species was formed that was structurally similar for each complex. The crystal structure of a representative new complex, [Mn(papy)(acac)] (H 2 papy = N-(2-hydroxybenzyl)-N -(2-picolyl)-glycine; Hacac = acetylacetone), was elucidated, demonstrating a Jahn-Teller distorted octahedral geometry of the Mn(III) ion. To gain insight into the reaction mechanisms by which these manganese complexes react with peroxides, the reaction of [Mn(pppy)(dpm)] with alkyl hydroperoxides was studied using UV-vis and EPR spectroscopy (H 2 pppy = 2-[bis(2-hydroxybenzyl)aminomethyl]-pyridine; Hdpm = dipivaloylmethane). It is proposed that in a reaction of [Mn(pppy)(dpm)] with t-butyl hydroperoxide ( t BuOOH), the species [Mn(III)(pppy)(OH)( t BuOO · )] is formed. In analogy with the formation of that species, which is postulated to occur through a reduction to Mn(II), it is proposed that in the direct initiation reaction of EL with a manganese(III) complex, a 1 electron-1 proton transfer reaction leads to the formation of Mn(II) and an EL radical. Considering parameters such as autoxidation activity, complex solubility and ease of complex preparation, the compound [Mn(III)(tbpppy)(dpm)] (H 2 tbpppy = 2-[bis(2-hydroxy-3,5-di-tert-butylbenzyl) aminomethyl]pyridine) is expected to be the best potential alkyd paint drier.

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Section: Synthesis and Characterisation Of Potential Drier Complexesmentioning

confidence: 58%

Section: Synthesis and Characterisation Of Potential Drier Complexesmentioning

confidence: 62%

Section: Methodsmentioning

confidence: 99%

Section: Synthesis and Characterisation Of Potential Drier Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

The autoxidation activity of new mixed-ligand manganese and iron complexes with tripodal ligands

Gorkum

Berding

Tooke

et al. 2007

Journal of Catalysis

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A Combined Experimental and Theoretical Study on Bis(μ‐alkoxo)diiron(III) Complexes with Hydroxybenzylaminoethanol [O,N,O] Donor Ligands: Syntheses, Structures and Magnetic Properties

et al. 2011

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Three new neutral bis(μ-alkoxo)diiron(III) complexes were prepared from N(R), N-(2-methylene-4,6-di-tert-butylphenol)aminoethan-1-ol ligands (H 2 L1, R = Me and H 2 L2, R = H). In these complexes, the ligand wraps around the metal center exhibiting a tridentate facial coordination mode with alkoxo-bridging oxygen, amine nitrogen and phenoxo oxygen donor atoms. In the complex [Fe(acac)L1] 2 ·MeCN (1) acetylacetonato coligand complete the distorted octahedral coordination spheres of the iron(III) ions, whereas in the five-coordinate iron(III) chloride complexes [FeClL1] 2 (2) and

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Synthesis, Structure, and C–C Cross‐Coupling Activity of (Amine)bis(phenolato)iron(acac) Complexes

2011

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A series of (amine)bis(phenolato)iron(III)acac complexes has been prepared and characterized. Reaction of Fe(acac)3 with the diprotonated linear tetradentate proligand N,N′‐bis(4,6‐di‐tert‐butyl‐2‐methylphenol)‐N,N′‐dimethyl‐1,2‐diaminoethane, H2[L1], and tripodal tetradentate ligand precursors dimethylaminoethylamino‐N,N‐bis(2‐methylene‐4,6‐di‐tert‐butylphenol), H2[L2], dimethylaminoethylamino‐N,N‐bis(2‐methylene‐4‐methyl‐6‐tert‐butylphenol), H2[L3], 2‐methoxyethylamino‐N,N‐bis(2‐methylene‐4,6‐di‐tert‐butylphenol), H2[L4], 2‐methoxyethylamino‐N,N‐bis(2‐methylene‐4‐methyl‐6‐tert‐butylphenol), H2[L5], and 2‐methoxyethylamino‐N,N‐bis(2‐methylene‐4,6‐dimethylphenol), H2[L6], produces the distorted octahedral FeIII complexes [L1]Fe(acac) (1), [L2]Fe(acac) (2), [L3]Fe(acac) (3), [L4]Fe(acac) (4), [L5]Fe(acac) (5), and [L6]Fe(acac) (6). In all of these complexes, the phenolato oxygen atoms are cis‐oriented. The paramagnetic FeIII complexes 1–6 were also characterized by UV/Vis and IR spectroscopy, mass spectrometry, cyclic voltammetry, and magnetic measurements. Single crystal X‐ray molecular structures have been determined for complexes 1, 2, 3, 5, and the proligand H2[L6]. Preliminary investigations of complexes 1–6 for catalytic cross‐coupling reactions of aryl Grignard reagents with cyclic and acyclic secondary alkyl halides and benzyl halides were performed. While the activity for cyclohexyl chlorides and bromides was high, cross‐coupling of benzyl halides was moderate and 2‐bromo‐ and 2‐chlorobutane gave poor yields of cross‐coupled product.

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The Synthesis, Structures and Characterisation of New Mixed‐Ligand Manganese and Iron Complexes with Tripodal, Tetradentate Ligands

Cited by 29 publications

References 45 publications

The autoxidation activity of new mixed-ligand manganese and iron complexes with tripodal ligands

The autoxidation activity of new mixed-ligand manganese and iron complexes with tripodal ligands

A Combined Experimental and Theoretical Study on Bis(μ‐alkoxo)diiron(III) Complexes with Hydroxybenzylaminoethanol [O,N,O] Donor Ligands: Syntheses, Structures and Magnetic Properties

Synthesis, Structure, and C–C Cross‐Coupling Activity of (Amine)bis(phenolato)iron(acac) Complexes

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