The synthesis and reaction kinetics of some Co(IIl) and Cr(III) chloro complexes of 1,4,8-Triazaoctane (2,3-tri) and the isolation of chiral trans-dichloro [CoCl2(NH3)(2,3-tri)] ClO4 |
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| Institution: | 1. Aix Marseille Univ, CNRS, ICR, UMR 7273, F-13397 Marseille, France;2. Département de Chimie, UFR des Sciences, Université de Versailles Saint-Quentin-en-Yvelines, Université Paris Saclay, 78035 Versailles, France;3. Institut Lavoisier de Versailles, UMR-CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, Université Paris Saclay, 78035 Versailles, France;4. Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires, UMR CNRS 8531, ENS Paris-Saclay, 94235 Cachan, France;5. Chimie et Interdisciplinarité: Synthèse, Analyse, Modélisation (CEISAM), UMR-CNRS 6230, Université de Nantes, 44322 Nantes, France;6. Université Paris Diderot, UFR de Chimie, 15 Rue Jean Antoine de Baïf, 75013 Paris, France;7. Research Fellow School of Science, RMIT University, Melbourne, 3001, VIC, Australia;8. Institut des Sciences Moléculaires d''Orsay (ISMO) - UMR 8214, Université Paris-Saclay, Université Paris-Sud, 91405 Orsay Cedex, France;9. Univ. Lille, CNRS, UMR 8516 - LASIR - Laboratoire de Spectrochimie Infrarouge et Raman, F-59000 Lille, France;1. R&D, Bharathiar University, Coimbatore 641 046, Tamil Nadu, India;2. Department of Chemistry, Muthayammal College of Arts and Science, Namakkal 637 408, Tamil Nadu, India;3. Department of Chemistry, Karunya Institute of Technology & Sciences, Coimbatore 641 114, Tamil Nadu, India;4. Nanotoxicology Research Lab, Department of Nanoscience, Karunya Institute of Technology & Sciences, Coimbatore 641 114, Tamil Nadu, India |
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| Abstract: | The reaction of 2,3-tri with CrCl3·6H2O1, dehydrated in boiling DMF, results in the formation of mer-CrCl3(2,3-tri) and anation of hydrolysed solutions of mer-MCl3(2,3,-tri) (M=Co, Cr) with 6 M HCl containing HClO4, forms trans-dichloro- mer-MCl2(2,3-tri)(OH2)]ClO4·H2O (M=Cr, Co; I, II). trans-Dinitro-mer-Co(NO2)2(NH3)(2,3-tri)] ClO4 crystallises from the reaction between mer-Co(NO2)3(2,3-tri) and aqueous 7 M ammonia, on addition of NaClO4·H2O, and trans-dichloro-mer-CoCl2(NH3)(2,3-tri)]ClO4 (III) can be isolated by treatment of the dinitro with 12 M HCl. Reaction of mer-CoCl3(2,3-tri) with C2O42−, followed by addition of aqueous NH3 and NaClO4·H2O results in the isolation of racemic mer-Co(ox)(NH3)(2,3-tri)]ClO4· H2O. This complex was resolved into its enantiomeric forms and treatment of these with SOCl2/MeOH/ HClO4 gave the chiral forms of trans-dichloro-mer- CoCl2(NH3)(2,3-tri)]ClO4 (R or S at the see-NH center). The rates of loss of the first chloro ligand from these dichloro complexes have been measured spectrophotometrically in 0.1 M HNO3 over a 15 K temperature range to give the following kinetic parameters; (I) kH(298)=7.25 × 10−5 s−1, Ea=78.5 kJ mol−1, δS298#=−69 J K−1 mol−1; (II) kH(298)=4.00 × 10−3 s−1, Ea=89.9, δS298#= +87.5; (III) kH(298)=3.09 × 10−4 s−1, Ea=103, δS298#=+27. Treatment of the dichloro cations with Hg2+/HNO3 results in the generation of mer- M(2,3-tri)(OH2)33+ (M=Cr, Co; IV, V) and trans- diaqua-mer-Co(NH3)(2,3-tri)(OH2)23+ (VI). The Co(III) cations isomerise to the fac configuration with (V) Kisom(298) μ=1.0 M)=2.97 × 10−5 s−1, Ea=115, δS298#=+46. (VI) Kisom(298) (μ=1.0 M)=4.13 × 10−5 s−1, Ea=113, δS298#=+52. |
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