Structural studies on [Mo3S4] and [Mo3S4Cu] complexes with tripodal ligands providing various NxOy (x + Y = 3) donor sets |
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Authors: | Kaspar Hegetschweiler Michael Wrle Marc D Meienberger Reinhard Nesper Helmut W Schmalle Robert D Hancock |
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Institution: | a Institut für Anorganische Chemie, Universität des Saarlandes, Postfach 15 11 50, D-66041, Saarbrücken, Germany b Laboratorium für Anorganische Chemie, ETH Zentrum, CH-8092, Zürich, Switzerland c Anorganisch Chemisches Institut der Universität Zürich, Winterhurerstrasse 190, CH-8057, Zurich, Switzerland d Centre for Molecular Design, Department of Chemistry, University of the Witwatersrand, WITS 2050, Johannesburg, South Africa |
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Abstract: | The interaction of 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and its N-methylated derivative 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci) with the incomplete Mo3S4]4+ cube and the heterometallic Mo3S4Cu]4+ cube have been investigated by X-ray analysis. The crystal structures of Mo3S4(taci+ rmC3H6O-H2O)3-4H]·2OH2O (1a, rhombohedral, space group R32, A = 15.964(3), C = 40.59(1) Å, Z = 6), Mo3S4(tdci)3]Br4·9.5EtOH·5H2O (2a, triclinic, space group and CuBrMo3S4(tdci)3]Br3·11 H2O·EtOH (3a, monoclinic, space group P2,/n, A = 14.887(3), B = 22.570(4), C = 21.974(5) Å, β = 98.54(2)°, Z = 4) revealed andN-N-O and an N-O-O coordination mode for taci and tdci, respectively. In 1a, taci is coordinated as an anion with deprotonated oxygen and nitrogen donors. In addition, the non-coordinating amino group reacted with one equivalent; of acetone, forming a Schiff base condensation product. For 2a, short Mo---O bonds and high pKa values (compared to the aqua ion Mo3S4(H2O)9]4+) indicate the formation of a zwitterionic form of the tdci ligand with coordinated alkoxo groups and peripheral dimethylammonium groups. No significant differences were found for the structural properties of the Mo-tdci fragment in 2a and 3a. The coordination modes of taci and tdci, as observed in the solid state, are in agreement with the previously reported solution structures, established by NMR spectroscopy. They are attributed to the specific steric requirements of the two ligands and to a pronounced preference of the Mo3(μS)3(μ3S)]4+ core to coordinate a nitrogen donor trans to μ3S. |
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Keywords: | Crystal structures Molybdenum complexes Polynuclear thio complexes Polyamine complexes Polyhydroxy complexes |
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