Single-crystal absorption spectroscopy of binuclear complexes of iron(III) and manganese(III) with the μ-oxo-bis(μ-acetato)dimetal core

Pelletier, Yanick; Reber, Christian

doi:10.1139/v95-034

Cited by 6 publications

(13 citation statements)

References 22 publications

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“…The complex [FeL 9 2 Cl] was readily synthesised by reaction of two equivalents of HL 9 with anhydrous iron(III) chloride in the presence of triethylamine. 24 The synthesis of achiral GaL 3 derivatives (L = bidentate Schiff base) from gallium isopropoxide has been reported 48 but surprisingly no syntheses from gallium chloride are available.…”

Section: Origins Of Diastereoselectionmentioning

confidence: 99%

“…Crystals of these three complexes were grown from benzenepentane (L 9 2 FeCl) toluene-pentane (L 9 2 GaCl) and hot heptane (L 10 2 GaCl). The complexes R C ,A M -[L 9 2 MCl] (M = Fe, Ga) are isomorphous, and the Ga compound only is shown in Fig. 11.…”

Section: Origins Of Diastereoselectionmentioning

confidence: 99%

“…Fig. 11 Molecular structure of R C ,A Ga -[GaL 9 2 Cl] with a-methylbenzyl groups shaded. The Fe complex is isomorphous.…”

Section: Origins Of Diastereoselectionmentioning

confidence: 99%

“…The m-oxo dimetal unit is a common motif of first row transition metal chemistry, [1][2][3][4][5][6][7][8][9][10][11] and many examples are known for tetradentate Schiff base complexes, 12-15 particularly for Fe (e.g. I), 16,17 porphyrins (e.g.…”

Section: Introductionmentioning

confidence: 99%

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Chirality and diastereoselection in the μ-oxo diiron complexes L2Fe–O–FeL2 (L = bidentate salicylaldiminato)

et al. 2010

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A number of bis(salicylaldiminato) (Schiff base) complexes of Fe(II) i.e. L(2)Fe with a variety of ligand substituents and functionality are synthesised, usually by salt metathesis but on one occasion via the (sal)(2)Fe complex, and characterised by standard methods. Two molecular structure determinations indicate the expected tetrahedral geometry. Treatment with dry oxygen yielded the Fe(III) complexes [(FeL(2))(2)-mu-O], generally in high yield and in the absence of hydroxylated impurities; one bulky complex L(2)Fe gave no oxidation product for steric reasons, and one hydroxyl-substituted compound gave an insoluble product. Five molecular structures of these [(FeL(2))(2)-mu-O] compounds were determined. All were homochiral in the sense that the absolute configuration at Fe was the same for both atoms. Three of the structures - those based on optically pure salicylaldimine ligands - were diastereomeric. For two, the diastereomers observed are those predicted on the basis of steric considerations, while a third highly distorted and congested structure represents the unexpected diastereomer. Powder X-ray diffraction confirms high phase purity of the bulk samples (i.e. they are diastereomerically pure to the level detectable). These investigations, coupled with molecular structure and NMR studies on model gallium complexes, indicate that the diastereoselection arises from cooperative interactions across the oxo bridge.

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Section: Origins Of Diastereoselectionmentioning

confidence: 99%

Section: Origins Of Diastereoselectionmentioning

confidence: 99%

“…Fig. 11 Molecular structure of R C ,A Ga -[GaL 9 2 Cl] with a-methylbenzyl groups shaded. The Fe complex is isomorphous.…”

Section: Origins Of Diastereoselectionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chirality and diastereoselection in the μ-oxo diiron complexes L2Fe–O–FeL2 (L = bidentate salicylaldiminato)

et al. 2010

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“…Articles within different fields of physics and chemistry demonstrate the broad and continued interest in exchange interactions in transition metal pairs. Published studies on Ni 2+ -Mn 2+ (Ferguson et al 1966a), Cu 2+ -Mn 2+ (Ferre and Regis 1978;Cador et al 2000), Mn 2+ -Mn 3+ (Franz et al 2004;Cox et al 2011;Xie et al 2012), Mn 3+ -Mn 3+ (Pelletier and Reber 1995), and Mn 3+ -Mn 4+ pairs (Birkelbach et al 1998) are some examples that reflect this interest.…”

Section: Optical Absorption Spectroscopymentioning

confidence: 98%

Color of Mn-bearing gahnite: A first example of electronic transitions in heterovalent exchange coupled IVMn2+-VIMn3+ pairs in minerals

Hålenius

Bosi

2014

American Mineralogist

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A natural yellow and transparent crystal of Mn-bearing, Mg-rich gahnite (ZnAl 2 O 4 ) from Nordmark (Sweden) was studied by electron microprobe, single-crystal X-ray diffraction and optical absorption spectroscopy. The empirical structural formula of the crystal, T (Zn 0.52 Mg 0.34 Mn 2+ 0.08 Al 0.06 ) S1.00 M (Al 1.88 Mn 3+ 0.06 Fe 3+ 0.01 Mg 0.04 Mn 2+ 0.01 ) S2.00 O 4 , shows that Mn 2+ and Mn 3+ are almost completely ordered at the T and M sites, respectively. The electronic absorption spectrum of the spinel shows, in addition to a strong UV-absorption edge (O 2--Mn 3+ and O 2--Fe 3+ ligand-metal charge transfers) and two broad VI Mn 3+ -bands, a set of relatively narrow absorption bands at energies comparable to those caused by spin-forbidden electron transitions in tetrahedrally coordinated Mn 2+ in oxide spinel. However, the set of bands in the present spectrum is shifted to lower energies and they are intensified by approximately an order of magnitude compared to those recorded for spin-forbidden IV Mn 2+ -bands in spinel. These characteristic differences in combination with the determined cation distribution in the present gahnite demonstrates that electronic transitions in exchange coupled IV Mn 2+ -VI Mn 3+ pairs cause its color.

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Manganese 1995

Vites¹,

Lynam²

1998

Coordination Chemistry Reviews

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Single-crystal absorption spectroscopy of binuclear complexes of iron(III) and manganese(III) with the μ-oxo-bis(μ-acetato)dimetal core

Cited by 6 publications

References 22 publications

Chirality and diastereoselection in the μ-oxo diiron complexes L2Fe–O–FeL2 (L = bidentate salicylaldiminato)

Chirality and diastereoselection in the μ-oxo diiron complexes L2Fe–O–FeL2 (L = bidentate salicylaldiminato)

Color of Mn-bearing gahnite: A first example of electronic transitions in heterovalent exchange coupled IVMn2+-VIMn3+ pairs in minerals

Manganese 1995

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