A series of five new dinuclear manganese(II/II) compounds with derivatives of 2-{[bis(pyridin-2-ylmethyl)amino]-methyl}phenol (HL 1 ) were synthesized and structurally characterized. All complexes crystallize in monoclinic space groups and exhibit Mn···Mn separations in the range of 3.392(8)−3.493(2) Å caused by bis(µ-phenoxo) bridging modes. The derivatives of HL 1 contain either electron-donating or -withdrawing substituents. A correlation between the electronic character of the different ring substituents, the

The synthesis and characterization of six novel mononuclear Mn(II) and Mn(III) complexes are presented. The tripodal ligands 2-((bis(pyridin-2-ylmethyl)amino)methyl)-4-nitrophenol (HL1), 2-[[((6-methylpyridin-2-yl)methyl)(pyridin-2-ylmethyl)amino]methyl]-4-nitrophenol (HL2), (2-pyridylmethyl)(6-methyl-2-pyridylmethyl)(2-hydroxybenzyl)amine (HL3) and 2-((bis(pyridin-2-ylmethyl)amino)methyl)-4-bromophenol were used. All ligands provide an N3O donor set. The compounds [Mn(II)(HL1)Cl2].CH3OH (1), [Mn(III)(L1)Cl2] (2), [Mn(II)(HL2)(EtOH)Cl2] (3), [Mn(II)(HL3)Cl2].CH3OH (4), [Mn(III)(HL4)Br2] (5) and [Mn(III)(L1)(tcc)] (6), with tcc = tetrachlorocatecholate dianion, were synthesized and characterized by various techniques such as X-ray crystallography, mass spectrometry, IR and UV-vis spectroscopy, cyclic voltammetry, and elemental analysis. Compound 1 crystallizes in the triclinic space group P1, compounds 2, 3 and 4 were solved in the monoclinic space group P2(1)/c, whereas the structure determination of and succeeded in the orthorhombic space groups Pbca and P2(1)2(1)2(1), respectively. Notably, the crystal structures of 1 and 3 are the first Mn(II) complexes featuring a non-coordinating phenol moiety. Compound 2 oxidizes 3,5-di-tert-butylcatechol to 3,5-di-tert-butylquinone exhibiting saturation kinetics at high substrate concentrations with a turnover number of kcat = 173 h(-1). The electronic influence of different substituents in para position of the phenol group is lined out.

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The tetranuclear manganese(II) complex [Mn 4 (ppi) 6 ](BPh 4 ) 2 (2) (Hppi ϭ 2-pyridylmethyl-2-hydroxyphenylimine) is prepared by using the precursor complex [Mn(ppi) 2 ]·H 2 O (1). Based on UV/Vis-and IR-spectroscopy data in combination with mass spectrometry it has been concluded that 1 is a mononuclear neutral Mn II complex, in which two ppi ligands chelate the manganese atom. Compound 2 crystallizes in the triclinic space group P1 (no. 2), with a ϭ 17.500 (3), b ϭ 17.955(4), c ϭ 19.101(4) Å , α ϭ 113.79(3)°, β ϭ 111.33(3)°, γ ϭ 93.91(3)°, V ϭ 4950(2) Å 3 and Z ϭ 2. In the tetranuclear [Mn 4 (ppi) 6 ] 2ϩ comEin vierkerniger Mangancluster mit einer sternförmigen Mn 4 O 6 -Kernstruktur: Gezielte Synthese mit einem mononuklearen Precursorkomplex Inhaltsübersicht. Mit der Darstellung von [Mn 4 (ppi) 6 ](BPh 4 ) 2 (2) (Hppi ϭ 2-Pyridylmethyl-2-hydroxyphenylimin) unter Verwendung des Precursorkomplexes [Mn(ppi) 2 ]·H 2 O (1) ist die gezielte Synthese eines vierkernigen Mangan(II)-Clusters gelungen. Anhand von UV/Vis-und IR-spektroskopischen Daten sowie des Massenspektrums wurde 1 als ein mononuklearer Mn II -Neutralkomplex identifiziert, in dem zwei ppi-Liganden das Manganion umgeben. Die Verbindung 2 kristallisiert im triklinen Kristallsystem in der Raumgruppe P1 (Nr. 2) mit a ϭ 17.500(3), b ϭ 17.955(4), c ϭ 19.101(4) Å , α ϭ 113.79(3)°, β ϭ 111.33(3)°, γ ϭ 93.91(3)°, V ϭ

The trinuclear manganese(II) complex [Mn 3 (ppi) 2 (µ-OAc) 4 (H 2 O) 2 ]·2MeOH (1) (Hppi ϭ 2-pyridylmethyl-2-hydroxyphenylimine) is prepared by dissolving two equivalents of Hppi (from the Schiff Base reaction of aminophenol and pyridine-2-carboxaldehyde) in acetonitrile and three equivalents of Mn(OAc) 2 ·4H 2 O in methanol and combining both solutions. The resulting red precipitate was recrystallized to yield red crystals suitable for single crystal X-ray diffraction. Compound 1 crystallizes in the triclinic space group P1 (no. 2), with a ϭ 9.691(2), b ϭ 10.683(2), c ϭ 11.541 (2) Å , Synthese und Charakterisierung von [Mn 3 (ppi) 2 (µ-OAc) 4 (H 2 O) 2 ] · 2MeOH ؊ Ungewöhnliche strukturelle Eigenschaften eines dreikernigen sauerstoffreichen Mangankomplexes Inhaltsübersicht. Der dreikernige Mangan(II)-Komplex [Mn 3 (ppi) 2 (µ-OAc) 4 (H 2 O) 2 ]·2MeOH (1) (Hppi ϭ 2-Pyridylmethyl-2-hydroxyphenylimin) konnte durch die Umsetzung von zwei Äquivalenten Hppi (aus der Schiff Base Reaktion von Aminophenol and Pyridin-2-carboxaldehyd), gelöst in Acetonitril und drei Äquivalenten Mn(OAc) 2 ·4H 2 O, gelöst in Methanol, dargestellt werden. Der entstehende Rückstand wurde umkristallisiert, um rote Einkristalle mit einer ausreichenden Qualität für eine Röntgenstrukturanalyse zu erhalten. Verbindung 1 kristallisiert in der triklinen Raum-