Synthesis,structure, and substitution reactivity of a new bi-oxo capped molybdenum cluster: [Mo3(μ3-O)2(μ-O2CCH2Cl)6(H2O)2(OH)]+ |
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| Affiliation: | 1. Department of Chemistry, California State University, Sacramento, 6000 J Street, Sacramento, CA 95819, USA;2. Department of Chemistry, University of California, Davis, One Shields Ave., Davis, CA 95616, USA;1. Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin 300387, People''s Republic of China;2. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300071, People''s Republic of China |
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| Abstract: | A new bi-oxo capped molybdenum carboxylate, Mo3(μ3-O)2(μ-O2CCH2Cl)6(H2O)2(OH)]+, was synthesized by refluxing Mo3(μ3-O)2(μ-O2CCH3)6(H2O)3]2 + in chloroacetic acid for 20 h (T = 110 °C). Using ion-exchange chromatography (0.5 M NaClO4 eluant), the trinuclear molybdenum ion was isolated and allowed to crystallize slowly (T = 4 °C) as the perchlorate salt (yield 23%). Upon dissolution of the compound in methanol-d4, substitution of the terminal ligands for solvent occurs readily in which the observed exchange rate constant is kobs298K = 5.3 × 10? 5 (± 0.3) s? 1 and activation parameters equal to ΔH3 = 130 (± 10) kJ mol? 1 and ΔS3 = 111 (± 33) J mol? 1 K? 1. From the kinetic data, we find that ligand substitution follows a dissociative pathway and that rates of substitution are faster than expected when compared to the molybdenum acetate analog. Herein, we report the synthesis, crystallographic study, and substitution reactivity of a new molybdenum bi-oxo capped cluster with bridging chloroacetate ligands. |
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