Manganese(II/II/II) and Manganese(III/II/III) Trinuclear Compounds. Structure and Solid and Solution Behavior

Vasilis Tangoulis; Dora A. Malamatari; Kali Soulti; Voula Stergiou; Catherine P. Raptopoulou; Aris Terzis; Themistoklis A. Kabanos; Dimitris P. Kessissoglou

doi:10.1021/ic960183j

Manganese(II/II/II) and Manganese(III/II/III) Trinuclear Compounds. Structure and Solid and Solution Behavior

Inorg Chem. 1996 Aug 14;35(17):4974-4983. doi: 10.1021/ic960183j.

Authors

Vasilis Tangoulis¹, Dora A. Malamatari, Kali Soulti, Voula Stergiou, Catherine P. Raptopoulou, Aris Terzis, Themistoklis A. Kabanos, Dimitris P. Kessissoglou

Affiliation

¹ Department of General & Inorganic Chemistry, Aristotle University of Thessaloniki, 54006 Thessaloniki, Greece, Department of Chemistry, Section of Inorganic and Analytical Chemistry, University of Ioannina, 45110 Ioannina, Greece, and NRCPS "Demokritos", Institute of Materials Science, 15310 Aghia Paraskevi Attikis, Greece.

PMID: 11666702
DOI: 10.1021/ic960183j

Abstract

Two mixed-valence Mn(III)Mn(II) complexes and a homo-valence Mn(II) trinuclear manganese complex of stoichiometry Mn(III)Mn(II)Mn(III)(5-Cl-Hsaladhp)(2)(AcO)(4)(MeOH)(2).4CH(3)OH (1a), Mn(III)Mn(II)Mn(III) (Hsaladhp)(2)(AcO)(2)(5-Cl-Sal)(2)(thf)(2) (3a) and Mn(II)Mn(II)Mn(II) (AcO)(6)(pybim)(2) (1b) where H(3)saladhp is a tridentate Schiff base ligand and pybim a neutral bidentate donor ligand, have been structurally characterized by using X-ray crystallography. The structurally characterized mixed-valence complexes have strictly 180 degrees Mn(III)-Mn(II)-Mn(III) angles as required by crystallographic inversion symmetry. The complexes are valence trapped with two terminal Mn(III) ions showing Jahn-Teller distortion along the acetate or salicylate-Mn(III)-X axis. The Mn.Mn separation is 3.511 Å and 3.507 Å respectively. The mixed-valence complexes have S = (3)/(2) ground state and the homovalence complex S = (5)/(2), with small antiferromagnetic exchange J couplings, -5.6 and -1.8 cm(-1), respectively, while the powder ESR spectra at 4 K show a broad low field signal with g approximately 4.3 for Mn(III)Mn(II)Mn(III) and a broad temperature-dependent signal at g = 2 for Mn(II)Mn(II)Mn(II). Crystal data for 1a: [C(36)H(60)O(20)N(2)Cl(2)Mn(3)], triclinic, space group P&onemacr;, a = 9.272(7) Å, b = 11.046(8) Å, c = 12.635(9) Å, alpha = 76.78(2) degrees, beta = 81.84(2) degrees, gamma = 85.90(2) degrees, Z = 1. Crystal data for 3a: [C(48)H(56)O(18)N(2)Cl(2)Mn(3)], monoclinic, space group P2(1)/n, a = 8.776(3) Å, b = 22.182(7) Å, c = 13.575(4) Å, beta = 94.44(1) degrees, Z = 2. Crystal data for 1b: [C(36)H(36)O(12)N(6)Mn(3)], triclinic, space group P&onemacr;, a = 13.345(6) Å, b = 8.514(4) Å, c = 9.494(4) Å, alpha = 75.48(1) degrees, beta = 75.83(1) degrees, gamma = 76.42(1) degrees, Z = 1.