The [Os(III)(CN)6]3- anion is prepared by chemical oxidation in aqueous solution and isolated as yellow prisms of [Ph4P]3[Os(III)(CN)6].6H2O (1). This species crystallizes in the triclinic space group P with cell parameters a = 13.7609(11) A, b = 16.2275(13) A, c = 17.0895(14) A, alpha = 91.4040(10) degrees , beta = 109.3600(10) degrees , gamma = 102.3970(10) degrees , V = 3497.4(5) A(3), and Z = 2. The slightly distorted octahedral moiety displays Os-C and C-N bond lengths that average 2.058 and 1.146 A, respectively. Spin-orbit-coupling splitting of the ground-state term dominates the NIR region of the electronic spectrum and the magnetic behavior of 1. The experimental information points to higher spin delocalization over the coordinated cyanides than in [Fe(III)(CN)6]3-.
Heterometallic compounds comprising copper() and rare-earth cations with carboxylate groups of the 2,2Јoxydiacetato as the connecting ligands, have been investigated. Five isostructural polymers 3), Nd (4) and Pr ( 5)) have been obtained and their structures determined by X-ray diffraction methods. The Ln() cations in 1 to 5 are coordinated by six carboxy and three ether oxygen atoms in the tricapped trigonal prism arrangement and the Cu() cations are bonded to four carboxy oxygens and two apical aqua ligands in a distorted octahedral geometry. The magnetic behaviors of these complexes show very weak antiferromagnetic interaction in the solid.
Twelve new withanolides were isolated from the aerial part of Jaborosa rotacea: five had a spiranoid delta-lactone (1-5); one contained a 26,12-delta-lactone and a C-12-C-23 bond (6); five corresponded to trechonolide-type withanolides with configuration at C-23 opposite of those previously isolated (7, 8, 10-12); two of these have an additional oxido-bridge between C-21 and C-24; finally a withanolide with a hemiketal ring formed between a 21-hydroxyl and a 12-ketone (13) and the closely related jaborosalactone R were also isolated. New compounds were fully characterized by a combination of spectroscopic methods (1D and 2D NMR and MS). The structures of the spiranoid withanolide and of the epimer of trechonolide A were confirmed by X-ray diffraction studies. Compounds 4, 5, 6, and 8 showed selective phytotoxicity toward monocotyledoneous and dicotyledoneous species.
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